Thiophene derivatives

ABSTRACT

Thiophene derivatives of the formula ##STR1## wherein X, Y and Z are as herein defined, said compounds being useful as fungicides, are described.

This invention relates to novel thiophene derivatives and to fungicides for agricultural and horticultural purposes which are characterized by containing as their active ingredients said derivatives. The novel thiophene derivatives prepared according to the present invention are represented by the general formula (I) ##STR2## wherein X represents hydrogen atom, alkali metal, NH₄, COR₁ (in which R₁ represents phenyl, halophenyl, lower alkyl, lower alkenyl, lower alkoxy lower alkyl, lower alkylthio lower alkyl, lower haloalkyl, ##STR3## cycloalkyl or lower alkylthio), --CO-lower alkyl-R₂ (in which R₂ represents lower alkylcarbonyloxy or lower alkoxycarbonyl), ##STR4## (in which n represents an integer of 4 to 6 inclusive), di-lower alkylcarbamoyl, mono-lower alkylcarbamoyl, cycloalkylcarbamoyl, --COOR₃ (in which R₃ represents lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower alkoxy lower alkyl, lower alkoxycarbonyl lower alkyl, phenyl, substituted phenyl or benzyl), --SO₂ R₄ (in which R₄ represents lower alkyl, lower alkyl-substituted phenyl or di-lower alkylamino) or ##STR5## (in which R₅ represents lower alkyl); Y represents --COOR₆ (in which R₆ represents alkyl, lower alkenyl, lower alkynyl, lower alkoxy lower alkyl or benzyl), hydrogen atom or ##STR6## (in which p represents hydrogen atom, halogen atom or lower alkyl); and Z represents COOR₆ (in which R₆ is as defined above), cyano or ##STR7## (in which p is as defined above), provided that both Y and Z are not --COOR₆ (in which R₆ represents alkyl, lower alkenyl or lower alkynyl) when X represents hydrogen atom, alkali metal or NH₄.

The term "lower", as used herein in connection with any alkyl, alkenyl or alkynyl portion is to mean that said portion as referred to contains one to four carbon atoms.

A sub-generic group of the particularly useful compounds of the invention can cover the compounds of the general formula (I), wherein X is a group --COR₁ (in which R₁ is lower alkyl, lower alkoxy lower alkyl, lower alkylthio lower alkyl), a group --COOR₃ (in which R₃ is lower alkyl) or mono-lower alkylcarbamoyl; Y is a group --COOR₆ (in which R₆ is lower alkyl, lower alkenyl or lower alkynyl) or a group ##STR8## (in which p is hydrogen or halogen); and Z is a group --COOR₆ as defined above.

The present inventors prepared by synthesis a large number of thiophene derivatives and extensively studied and invenstigated on practical usefulness of these thiophene derivatives as fungicides for agricultural and horticultural purposes. As a result, it has been found that novel compounds represented by the aforesaid general formula (I) are broadly and divergently usable as fungicides for agricultural and horticultural purposes, exhibiting their controlling activity against various plant deseases such as rice blast, rice brown spot, rice sheath blight, tomato late blight, haricot sclerotinia rot, rice `Bakanae` disease, cucumber Fusarium wilt, tomato leaf mold, grape ripe rot, pear black spot, Japanese apple canker, vegetable soft rot, rice bacterial blight, cucumber bacterial spot, cucumber downy mildew, cucumber powdery mildew, cucumber anthracnose, etc.

The compounds of the general formula (I) of the present invention can be prepared according to processes represented by the following reaction formulas, respectively. ##STR9## wherein A is alkyl, lower alkenyl, lower alkynyl, lower alkoxy lower alkyl or benzyl; and Y and Z are individually defined as previously.

The instant reaction can be carried out in an organic solvent such as alcohol, ether, hydrocarbon, DMF (dimethylformamide), etc., in the presence of a deprotonating reagent such as metallic sodium, sodium hydride, butyl lithium, alkali metal alcoholate, etc., at a temperature of 0°-100° C. for 2-24 hours. The reaction mixture can be worked up by pouring it into ice water and then acidifying the resulting mixture with hydrochloric acid, sulfuric acid or the like mineral acid, thereby to have the desired 3,4-dihydroxythiophene derivative separated out. ##STR10## wherein X, Y and Z are individually as defined previously provided that X is not hydrogen, and Hal represents halogen atom.

The above reaction can be carried out in an inert solvent such as dioxane, acetone, benzene, DMF, etc., in the presence of a dehydrohalogenating agent such as triethylamine, pyridine, potassium carbonate, sodium carbonate, etc., at a temperature of 0° to 150° C. for 1-24 hours. After the reaction, the resulting mixture is poured into water and then worked up by filtration, extraction or the like procedures to obtain the intended thiophene derivative.

(2') The compounds of the above formula (I) wherein X is COR₁ (in which R₁ is lower alkyl) can be prepared by the following reaction: ##STR11## The above reaction can be achieved at a temperature of 30° to 140° C. for 2-16 hours, with or without using a solvent, e.g. benzene, acetic acid, chloroform, ether, etc. by removing an acid formed during the reaction.

(2") The compounds of the formula (I) wherein X is mono-lower alkylcarbamoyl can be prepared by the following reaction: ##STR12## The above reaction is carried out in an inert solvent such as dioxane, benzene, DMF, etc., in the presence of a catalytic amount of triethylamine or the like organic base at a temperature of from room temperature to 80° C. for 2-24 hours. The resulting reaction mixture can be worked up in the similar manner as mentioned above.

Illustrative of the synthesis of the compounds of the present invention are mentioned below with reference to examples.

EXAMPLE 1 3,4-Diacethoxy-2,5-di-n-propoxycarbonylthiopene (Compound No. 3)

A mixture comprising 57.6 g (0.2 mol) of 3,4-dihydroxy-2,5-di-n-propoxycarbonyl-thiophene, 60 ml of acetic anhydride and 1 g of sodium acetate is stirred at about 40° C. to undergo reaction, whereupon the reaction liquid shows pale brown. The reaction is continued at 60°-80° C. for additional 2 hours. Into the reaction liquid having been allowed to cool is poured 500 ml of ice-cooled water, whereby crystals are deposited. The crystal collected by filtration and washed with water are then recrystallized from 60 ml of methanol to give 59 g of the title compound as colorless prisms, m.p. 46°-48° C.

EXAMPLE 2 3,4-Bis(N-methylcarbamoyloxy)-2,5-dicarbethoxy-thiophene (Compound No. 50)

To a solution of 100 g (0.384 mol) of 3,4-dihydroxy-2,5-dicarbethoxy-thiophene in 350 ml of dioxane are added 55 g (0.96 mol) of methyl isocyanate and 10 drops of triethylamine, and the resulting mixture is stirred, whereupon an exothermic reaction occurs and the internal temperature rises to 50°-60° C. The reaction is continued, as it is, for 8 hours (in this case the reaction may be carried out by warming the reaction liquid). After the reaction liquid is allowed to cool, the deposited crystals were collected by filtration and washed with n-hexane, whereupon the title compound is obtained as colorless crystals, m.p. 152°-153° C. The yield 117 g.

EXAMPLE 3 3,4-Dimethoxycarbonyloxy-2,5-dicarbethoxy-thiophene (Compound No. 22)

To a solution of 7.8 g (0.03 mol) of 3,4-dihydroxy-2,5-dicarbethoxy-thiophene in a mixture of 10 g (0.1 mol) of pyridine and 100 ml of benzene is added dropwise while cooling with ice 14.5 g (0.066 mol) of methyl chlorocarbonate in a period of 1.5 hours. The reaction liquid is brought back to room temperature and then stirred for additional 2 hours to terminate the reaction. The reaction liquid is washed with water, dilute solution of sodium hydroxide, dilute hydrochloric acid, and water in that order, dried over sodium sulfate and then concentrated. The concentrate is charged with n-hexane and cooled with ice to deposit crystals. On collecting the deposited crystals by filtration, the title compound is obtained as colorless prisms, m.p. 87°-88° C. The yield 6.5 g.

EXAMPLE 4 3,4-Bis(diethoxythiophophoryloxy)-2,5-dicarbethoxy-thiophene (Compound No. 108)

In a solution of 2.6 g (0.01 mol) of 3,4-dihydroxy-2,5-dicarbethoxy-thiophene in 60 ml of acetone is suspended with stirring 2.8 g (0.02 mol) of sodium carbonate. The suspension was charged with 4.2 g (0.022 mol) of diethyl chlorothiophosphate, and the mixture is heated under reflux for 3 hours. After allowing the reaction liquid to cool, the solvent is distilled off, and the residue is dissolved in benzene. On distilling off the solvent, the title compound is obtained as colorless glass-like flakes, m.p. 105.6° C. The yield 1.7 g.

EXAMPLE 5 3,4-Dihydroxy-2,5-di-2'-ethoxyethoxycarbonylthiophene (Compound No. 159)

Into a mixture of 150 ml of 2-ethoxyethanol and 100 ml of DMF is added with ice-cooling 18 g (0.45 mol) of NaH (60%) powder, and thereto is then added dropwise at room temperature to 80° C. a mixed liquid of 54 g (0.2 mol) of diethoxyethyl ester of thiodiglycolic acid and 63 g (0.3 mol) of diethoxyethyl ester of oxalic acid, followed by stirring at 60°-80° C. for additional 1 hour. The reaction liquid is poured into 50 ml (0.5 mol) of concentrated hydrochloric acid and 500 ml of water, and the deposited crystals are separated by filtration. Recrystallization from aqueous methanol to give 33.2 g (48% yield) as yellow powder, m.p. 79°-80° C.

Elemental analysis (for C₁₄ H₂₀ O₈ S): Calculated (%): C 48.27; H 5.79. Found (%): C 50.00; H 5.90.

EXAMPLE 6 3,4-Di-methylcarbamoyloxy-2,5-di-2'-ethoxyethoxycarbonylthiophene (Compound No. 161)

To a solution of 3.5 g (0.01 mol) of 3,4-dihydroxy-2,5-di-2'-ethoxyethoxycarbonylthiophene and 1.2 g (0.02 mol) of methyl isocyanate is added 0.1 ml of triethylamine, and the mixture is stirred at room temperature for 7 hours. The reaction liquid is then poured into 100 ml of water, and the deposited crystals were separated by filtration. Recrystallization from a mixed solvent of n-hexane and benzene gives 2.1 g (46% yield) of the title compound as white needles, m.p. 87.5° C.

Elemental analysis (for C₁₈ H₂₆ N₂ O₁₀ S): Calculated (%): C 46.75; H 5.63; N 6.06. Found (%): C 46.90; H, 5.65; N 5.70.

EXAMPLE 7 3,4-Di-methoxymethylcarbonyloxy-2,5-di-2'-methoxyethoxycarbonylthiophene (Compound No. 170)

To a solution of 3.2 g (0.01 mol) of 3,4-dihydroxy-2,5-di-2'-methoxyethoxycarbonylthiophene and 3.0 g (0.028 mol) of methoxyacetyl chloride in 50 ml of dioxane is added dropwisw with ice-cooling 10 ml of triethylamine, and the mixture, after being stirred for 30 minutes, is allowed to undergo reaction at room temperature for additional 1 hour. The reaction liquid is poured into 200 ml of water, and the deposited crystals are separated by filtration. Recrystallization from ethanol to give 1.6 g (35% yield) of the title compound as white needles, m.p. 81.2° C.

Elemental analysis (for C₁₈ H₂₄ O₁₂ S): Calculated (%): C 46.55; H 5.17. Found (%): C 46.55; H 5.10.

EXAMPLE 8 3,4-Di-methoxycarbonyloxy-2,5-dibenzyloxycarbonylthiophene (Compound No. 179)

To a solution of 3.8 g (0.01 mol) of 3,4-dihydroxy-2,5-di-benzyloxycarbonylthiophene and 2.2 g (0.023 mol) of methyl chloroformate in 20 ml of dioxane is added 5 ml of pyridine, and the mixture is heated with stirring at 60° C. for 2 hours. After completion of the reaction, the reaction liquid is poured into 150 ml of water, and the deposited crystals are separated by filtration. Recrystallization from ethanol gives 3.2 g (64% yield) of the title compound as white plate-like flakes, m.p. 103.4° C.

Elemental analysis (for C₂₄ H₂₀ O₁₀ S): Calculated (%): C 57.60; H 4.00. Found (%): C 57.60; H 4.00.

EXAMPLE 9 3,4-Dihydroxy-2-cyano-5-carbethoxythiophene (Compound No. 210)

A solution of 18.5 g (0.126 mol) of ethyl ester of oxalic acid and 20 g (0.126 mol) of ethyl ester of cyanomethylthioglycolic acid in 50 ml of ethanol is maintained on an ice bath at 2° C. Subsequently, to the solution is gradually added dropwise a sodium ethylate solution prepared by treating 7.3 g (0.315 mol) of metallic sodium with 120 ml of dry ethanol, and the mixture is allowed to undergo reaction for 30 minutes. During that period of time, the reaction temperature is maintained at 2°-5° C. After completion of the reaction, the reaction liquid is allowed to stand in a refrigerator for 2 days, whereupon Na salt is deposited as crystals. The crystals collected is dissolved in 50 ml of water and acidified with hydrochloric acid. Recrystallization from acetic acid to give 14.0 g of the title compound as colorless crystals, m.p. 177°-180° C. (decomposition).

Elemental analysis (for C₈ H₇ O₄ NS): Calculated (%): C 45.06; H 3.31; N 6.57. Found (%): C 44.80; H 3.26; N 6.51.

    ______________________________________                                         H.sup.1 --NMR:                                                                            δ (ppm)                                                                           1.4      (C--CH.sub.3)                                                                           3H                                                  δ (ppm)                                                                           4.4      (O--CH.sub.2 --)                                                                        2H                                                  δ (ppm)                                                                           11.1     (--OH)   2H                                       ______________________________________                                    

EXAMPLE 10 3,4-Di(N-ethylcarbamoxyloxy)-2-cyano-5-methoxycarbonylthiophene (Compound No. 208)

One (1) drop of triethylamine is added to a solution in 20 ml of DMF of 1 g (0.005 mol) of 3,4-dihydroxy-2-cyano-5-methoxycarbonylthiophene which has been synthesized in the same manner as in Example 1, and thereot is added dropwise at room temperature 1.5 g of (0.02 mol) of ethyl isocyanate and thereby to effect reaction. The reaction system is warmed for 20 minutes to terminate the reaction, and the reaction liquid is poured into water, whereupon crystals are deposited. Recrystallization from ethanol give 0.4 g of the title compound as colorless crystals, m.p. 118°-121° C.

    ______________________________________                                         H'NMR:     δ (ppm)                                                                           1.2       (CCH.sub.3)                                                                             6H                                                 δ (ppm)                                                                           3.3       (NCH.sub.2)                                                                             4H                                                 δ (ppm)                                                                           3.9       (OCH.sub.3)                                                                             3H                                                 δ (ppm)                                                                           5.5                                                                                       ##STR13##                                                                              2H                                      ______________________________________                                    

EXAMPLE 11 3,4-Di-acethoxy-2-cyano-5-carbethoxythiophene (Compound No. 212)

In 10 ml of acetic anhydride, 1.5 g (0.007 mol) of 3,4-dihydroxy-2-cyano-5-carbethoxythiophene is refluxed for 2 hours. After allowing to cool, the reaction liquid is poured into water, whereupon crystals are deposited which are then separated by filtration. Recrystallization from ethanol-water to give 1.4 g of the title compound as colorless crystals, m.p. 92°-94° C.

    ______________________________________                                         H'NMR:     δ (ppm)                                                                           1.3       (CCH.sub.3)                                                                             3H                                                 δ (ppm)                                                                           2.4                                                                                       ##STR14##                                                                              6H                                                 δ (ppm)                                                                           4.4       (OCH.sub.2)                                                                             2H                                      ______________________________________                                    

EXAMPLE 12 3,4-Di-(ethylcarbonyldioxy)-2-cyano-5-carbethoxythiophene (Compound No. 216)

To a solution in 30 ml of dioxane of 2 g (0.0094 mol) of 3,4-dihydroxy-2-cyano-5-carbethoxythiophene is added 10 ml of pyridine, and thereto is added dropwise with cooling 3.1 g (0.028 mol) of ethyl chloroformate, whereupon pyridine hydrochloride is immediately deposited. The reaction liquid is stirred, as it is, for 2 hours and then allowed to stand overnight.

The reaction liquid is poured into 200 ml of cold water and then acidified with hydrochloric acid, whereupon crystals are desposited which are then separated by filtration. Recrystallization from ethanol-water to give 2.3 of the title compound as colorless needles, m.p. 53°-54° C.

    ______________________________________                                         H'--NMR:  δ (ppm)                                                                           1.3-1.5   (C--CH.sub.3)                                                                           9H                                                 δ (ppm)                                                                           4.3-4.6   (O--CH.sub.2 --)                                                                        6H                                       ______________________________________                                    

EXAMPLE 13 3,4-Dihydroxy-2-carbomethoxy-5-benzoylthiophene (Compound No. 246)

To an ice-cold solution of 130 g (0.30 mol) of normal butyl lithium (a 15% n-hexane solution) in 400 ml of dry ether is added dropwise with stirring a mixed solution of 27 g (0.12 mol) of methyl ester of phenacylthioglycolic acid and 28 g (0.24 mol) of dimethyl oxalate in 50 ml of dry dioxane and 100 ml of dry ether in a period of about 1 hour. After completion of the addition, the reaction liquid is stirred with ice-cooling for additional 1 hour and then brought back to room temperature, followed by standing for one day. The precipitate thus formed is separated by filtration, washed with a small amount of ether and then dissolved in a possible small amount of acetone. The solution is diluted with water to 5 to 6 times, acidified with dilute hydrochloric acid, salted out with sodium chloride and extracted with a mixed solvent of benzene and ethyl acetate. The organic layer formed is dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove the solvent therefrom. The residue obtained is crystallized from a mixed solvent of benzene and n-hexane to obtain 6.2 g (26% yield) of the title compound as yellow fine powder, m.p. 136°-138° C.

    ______________________________________                                         NMR:    δ (ppm)                                                                                8.2-8.4   Aromatic                                                                              2H                                              δ (ppm)                                                                                7.7-8.0   Aromatic                                                                              3H                                              δ (ppm)                                                                                4.1       O--CH.sub.3                                            δ (ppm)                                                                                9.6       OH                                                     δ (ppm)                                                                               12.3       OH                                             ______________________________________                                    

EXAMPLE 14 3,4-Dihydroxy-2-carbethoxy-5-benzoylthiophene (Compound No. 247)

To an ice-cold solution of 53 g (0.13 mol) of normal butyl lithium (a 15% n-hexane solution) in 200 ml of dry ether is gradually added dropwise with stirring a mixed solution of 12 g (0.05 mol) of ethyl ester of phenacylthioglycolic acid and 15 g (0.10 mol) of diethyl oxalate in 50 ml of dry ether in a period of about 1 hour. After completion of the addition, the reaction liquid is stirred with ice-cooling for additional 30 minutes and then brough back to room temperature, followed by standing for one day. The deposited precipitate is separated by filtration, washed with a small amount of ether and then dissolved in a possible small amount of acetone. The solution is diluted with water to 5 to 6 times, acidified with dilute hydrochloric acid, salted out with sodium chloride and extracted with a mixed solvent of benzene and ethyl acetate. The organic layer formed is dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove the solvent therefrom. The residue obtained is crystallized from a mixed solvent of benzene and n-hexane to obtain 3.2 g (23% yield) of the title compound as yellow microcrystals, m.p. 147°-148° C.

    ______________________________________                                         IR (cm.sup.-1)                                                                            °3300 cm.sup.-1                                                                         Enolic OH                                                      °1680 cm.sup.-1                                                                         COOEt                                                          °1600 cm.sup.-1                                                                          ##STR15##                                          ______________________________________                                    

    ______________________________________                                         NMR:    δ (ppm)                                                                                8.0-8.2  Aromatic                                                                               2H                                              δ (ppm)                                                                                7.5-7.9  Aromatic                                                                               3H                                              δ (ppm)                                                                                4.4-4.6  O--CH.sub.2 --                                          δ (ppm)                                                                                1.3-1.6  C--CH.sub.3                                             δ (ppm)                                                                                9.45     OH                                                      δ (ppm)                                                                               11.8      OH                                              ______________________________________                                    

EXAMPLE 15 3,4-Dihydroxy-2-benzoylthiophene (Compound No. 250)

To an ice-cold sodium ethoxide solution prepared from 3.8 g (0.17 mol) of metallic sodium and 200 ml of ethanol is added dropwise with stirring in a period of about 1 hour a mixed solution of 13 g (0.055 mol) of ethyl ester of phenacylthioglycolic acid and 16 g (0.11 mol) of diethyl oxalate in 50 ml of ethanol. After completion of the addition, the ice bath is withdrawn and the reaction liquid is stirred at room temperature for 2 hours. Thereafter, the reaction liquid is poured into saline water, acidified with dilute hydrochloric acid and then extracted with a mixed solvent of benzene and ethyl acetate. The organic layer separated is extracted twice with a dilute aqueous sodium hydroxide solution. The alkaline layer thus formed is acidified with dilute hydrochloric acid and extracted with a mixed solvent of benzene and ethyl acetate. The organic layer obtained is dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove the solvent therefrom, and the residue obtained is crystallized from a small amount of a mixed solvent of benzene and n-hexane to obtain 1.0 g (9% yield) of the title compound as brown powder, m.p. 152°-154° C. (decomp.).

    ______________________________________                                         NMR:    δ (ppm)                                                                               8.2-8.3    Aromatic                                                                              2H                                              δ (ppm)                                                                               7.5-8.0    Aromatic                                                                              3H                                              δ (ppm)                                                                               7.4        H                                                      δ (ppm)                                                                               9.5-11.4   2OH                                            ______________________________________                                    

EXAMPLE 16 3,4-Dihydroxy-2,5-dibenzoylthiophene (Compound No. 265)

To an ice-cold solution of 55 g (0.13 mol) of normal butyl lithium (a 15% n-hexane solution) in 200 ml of dry ether is gradually added dropwise with stirring in a period of about 1 hour a mixed solution of 13.5 g (0.05 mol) of diphenacyl sulfide and 15 g (0.12 mol) of diethyl oxalate in 50 ml of dry ether. After completion of the addition, the reaction liquid is stirred for 30 minutes, brought back to room temperature and allowed to stand overnight. The reaction liquid is charged with 200 ml of n-hexane and thoroughly stirred, and the precipitate deposited is separated by filtration, washed with a small amount of ether and dissolved in a possible small amount of acetone. The solution is diluted to 5 to 6 times with water, acidified with dilute hydrochloric acid, salted out with sodium chloride and extracted with a mixed solvent of benzene and ethyl acetate. The organic layer obtained is then extracted with a dilute aqueous sodium hydroxide solution. The alkaline layer thus obtained is acidified with dilute hydrochloric acid and extracted with a mixed solvent of benzene and ethyl acetate. The organic layer obtained is dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove the solvent therefrom. The residue obtained is crystallized with a small amount of a mixed solvent of benzene and n-hexane to obtain 1.6 g (10% yield) of the title compound as yellow microgranules, m.p. 179°-181° C.

    ______________________________________                                         NMR:    δ (ppm)                                                                                8.2-8.4   Aromatic                                                                              4H                                              δ (ppm)                                                                                7.6-8.1   Aromatic                                                                              6H                                              δ (ppm)                                                                               12.15      2OH                                            ______________________________________                                    

EXAMPLE 17 3,4-Diacetoxy-2-carbethoxy-5-benzoylthiophene (Compound No. 249)

To an ice-cold solution of 1.3 g (0.0045 mol) of 3,4-dihydroxy-2-carbethoxy-5-benzoylthiophene in a mixture of 10 ml of pyridine and 20 ml of dioxane is added dropwise with stirring 1.8 g (0.023 mol) of acetyl chloride. The mixture is stirred, as it is, for 30 minutes and thereafter at room temperature for 1 hour. The reaction liquid is poured into ice-cold water and extracted with benzene. The extract is dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove the solvent therefrom. The residue obtained is subjected to silica gel column chromatography with a mixed solvent of benzene and ethyl acetate to give 0.6 g (36% yield) of the title compound as a viscous reddish brown liquid, n_(d) ²² 1.5710.

    ______________________________________                                         NMR:    δ (ppm)                                                                               7.8-7.9   Aromatic                                                                               2H                                              δ (ppm)                                                                               7.4-7.7   Aromatic                                                                               3H                                              δ (ppm)                                                                               4.3-4.5   OCH.sub.2                                               δ (ppm)                                                                               1.2-1.5   CHCH.sub.3                                              δ (ppm)                                                                               2.0                                                                                       ##STR16##                                              δ (ppm)                                                                               2.3                                                                                       ##STR17##                                      ______________________________________                                    

EXAMPLE 18 3,4-Di(methylcarbonyldioxy)-2-carbethoxy-5-benzoylthiophene (Compound No. 252)

To a solution of 0.5 g (0.0017 mol) of 3,4-dihydroxy-2-carbethoxy-5-benzoylthiophene in 20 ml of dioxane is added 0.6 g (0.006 mol) of triethylamine, and the mixture is ice-cooled. To the ice-cooled mixture is added with stirring 0.6 g (0.0063 mol) of methyl chloroformate, and the mixture is stirred, as it is, for 10 minutes and thereafter at room temperature for additional 1 hour. The reaction liquid is then poured into ice-cold water and extracted with chloroform, and the extract is dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove the solvent therefrom. The residue obtained is subjected to silica gel column chromatography with a mixed solvent of benzene and ethyl acetate to give 0.6 g (90% yield) of the title compound as a pale brown viscous liquid n_(D) ²¹ 1.5510.

    ______________________________________                                         NMR:    δ (ppm)                                                                             8.0-8.2  Aromatic   2H                                              δ (ppm)                                                                             7.6-7.9  Aromatic   3H                                              δ (ppm)                                                                             4.4-4.7  COOCH.sub.2                                                δ (ppm)                                                                             1.3-1.5  COOCH.sub.2CH.sub.3                                        δ (ppm)                                                                             3.9                                                                                      ##STR18##                                                 δ (ppm)                                                                             4.1                                                                                      ##STR19##                                         ______________________________________                                    

EXAMPLE 19 3,4-Di(N,N-dimethylcarbamoyloxy)-2-carbethoxy-5-(p-methylbenzoyl)-thiophene (Compound No. 287)

To a solution of 1 g (0.0033 mol) of 3,4-dihydroxy-2-carbethoxy-5-(p-methylbenzoyl)thiophene in 30 ml of benzene are added 1 g (0.01 mol) of triethylamine and 0.9 g (0.008 mol) of N,N-dimethylcarbamoyl chloride, and the mixture is heated with stirring at 50°-70° C. for 3 hours. The reaction liquid is then washed with water, dried over anhydrous sodium sulfate, and distilled under reduced pressure to remove the solvent therefrom. The residue obtained is subjected to silica gel chromatography with a mixed solvent of benzene and ethyl acetate to give 1.2 g (82% yield) of the title compound as a reddish brown liquid, n_(D) ²⁵ 1.5382.

    ______________________________________                                         NMR:    δ (ppm)                                                                             2.45                                                                                     ##STR20##                                                 δ (ppm)                                                                             7.8-7.9  Aromatic   2H                                              δ (ppm)                                                                             7.3-7.4  Aromatic   2H                                              δ (ppm)                                                                             4.3-4.5  COOCH.sub.2                                                δ (ppm)                                                                             1.3-1.4  COOCH.sub.2CH.sub.3                                        δ (ppm)                                                                             2.8                                                                                      ##STR21##                                                 δ (ppm)                                                                             3.1-3.2                                                     ______________________________________                                    

EXAMPLE 20 3,4-Di(methanesulfonyloxy)-2-carbethoxy-5-benzoylthiophene (Compound No. 290)

To a solution of 0.6 g (0.0020 mol) of 3,4-dihydroxy-2-carbethoxy-5-benzoylthiophene in 50 ml of benzene are added 0.8 g of triethylamine and 0.8 g (0.007 mol) of methanesulfonyl chloride, and the mixture is stirred for 2 hours while warming at 50°-70° C. to undergo reaction. The reaction liquid is then washed successively with a dilute aqueous sodium hydroxide solution and then with water. The benzene layer separated is dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove the solvent therefrom. The residue obtained is subjected to silica gel chromatography with a mixed solvent of benzene and ethyl acetate to give 0.4 g (45% yield) of the title compound as a brown liquid, n_(D) ²⁵ 1.5439.

    ______________________________________                                         Mass spectrum (m/e)                                                                         448      Parent peak (P)                                                       369      P-79 (CH.sub.3 SO.sub.2)                                              323      P-125 (CH.sub.3 SO.sub.2 + C.sub.2 H.sub.5 OH)                        105                                                                                      ##STR22##                                                             77                                                                                      ##STR23##                                               ______________________________________                                    

EXAMPLE 21 3,4-Di(2'-ethoxyethylcarbonyloxy)-2,5-dicarbethoxy-thiophene (Compound No. 295)

To an ice-cold solution of 3.9 g (0.015 mol) of 3,4-dihydroxy-2,5-dicarbethoxythiophene and 5.0 g (0.037 mol) of 2-ethoxy-propionyl chloride in 50 ml of dioxane is added dropwise with stirring 15 ml of triethylamine. After completion of the addition, the mixture is heated at 60° C. for 1 hour. The reaction liquid is then poured into 150 ml of water and extracted with 200 ml of benzene. The extract is dried over anhydrous sodium sulfate and then distilled under reduced pressure to remove the solvent therefrom, whereby 4.9 g of the title compound is obtained as a yellowish brown viscous liquid, n_(D) ²⁵.5 1.4929.

Elemental analysis (for C₁₈ H₂₈ O₈ S): Calculated (%): C 46.96; H 6.09. Found (%): C 46.91; H 6.07.

EXAMPLE 22 3,4-Di-(2'-furoyloxy)-2,5-dicarbethoxythiophene (Compound No. 296)

To an ice-cold solution of 2.6 g (0.01 mol) of 3,4-dihydroxy-2,5-dicarbethoxythiophene and 3.1 g (0.024 mol) of furoyl chloride in 50 ml of dioxane is added dropwise with stirring 10 ml of triethylamine. After completion of the addition, the mixture is heated at 60° C. for 1 hour. The reaction liquid is then poured into 200 ml of water, and the deposited crystals are separated by filtration. Recrystallization from ethanol gives 3.8 g (85% yield) of the title compound as white needles, m.p. 137.1° C.

Elemental analysis (for C₂₂ H₁₈ O₁₀ S): Calculated (%): C 58.93; H 4.02. Found (%): C 58.85; H 4.05.

EXAMPLE 23 3,4-Di-(2'-thenoyloxy)-2,5-dicarbethoxythiophene (Compound No. 299)

To an ice-cold solution of 3.9 g (0.015 mol) of 3,4-dihydroxy-2,5-dicarbethoxy-thiophene and 5.3 g (0.036 mol) of thenoyl chloride in 50 ml of dioxane is added dropwise with stirring 15 ml of triethylamine. After completion of the addition, the mixture is stirred at 60° C. for 1 hour. The reaction liquid is then poured into 200 ml of water, and the deposited crystals are separated by filtration. Recrystallization from ethanol gives 5.3 g (74% yield) of the title compound as white columns, m.p. 132.8° C.

Elemental analysis (for C₂₂ H₁₈ O₈ S₃): Calculated (%): C 55.23; H 3.77. Found (%): C 55.18; H 3.81.

Exemplified below in Tables 1a through 1e are the compounds of the present invention as prepared according to the procedures described in the foregoing examples. The compound number assigned to each compound in the tables will be referred to in examples and test examples that follow.

                                      TABLE 1a                                     __________________________________________________________________________      ##STR24##                                                                                                   Physicochemical                                                                data                                                                           [m.p. (°C.) or                            Compound                      refractive                                       No.    OX          COOR.sub.6 index n.sub.D ]                                  __________________________________________________________________________     1      OCOCH.sub.3 COOCH.sub.3                                                                               m.p. 106.8                                       2        "         COOC.sub.2 H.sub.5                                                                        m.p. 82-83                                       3        "         COOC.sub.3 H.sub.7n                                                                       m.p. 46-48                                       4        "         COOC.sub.3 H.sub.7i                                                                       m.p. 87.1                                        5        "         COOC.sub.4 H.sub.9n                                                                       n.sub.D.sup.23 1.4991                            6        "         COOC.sub.4 H.sub.9i                                                                       n.sub.D.sup.28 1.4945                            7        "         COOCH.sub.2 CHCH.sub.2                                                                    m.p. 67-68                                       8      OCOOCH.sub.3                                                                               COOCH.sub.2 CCH                                                                           n.sub.D.sup.21 1.5191                            9      OCOCH.sub.3 COOC.sub.6 H.sub.13n                                                                      n.sub.D.sup.21 1.4658                            10     OCOC.sub.2 H.sub.5                                                                         COOC.sub.2 H.sub.5                                                                        n.sub. D.sup.30 1.4985                           11     OCOC.sub.3 H.sub.7i                                                                          "        n.sub.D.sup.29 1.4935                            12     OCOC.sub.4 H.sub.9n                                                                        COOC.sub.2 H.sub.5                                                                        n.sub.D.sup.26.5 1.4943                          13       "         COOC.sub.3 H.sub.7n                                                                       n.sub.D.sup.27 1.4884                            14       "         COOC.sub.4 H.sub.9i                                                                       n.sub.D.sup.27 1.4740                            15     OCOCHCHCH.sub.3                                                                            COOC.sub.2 H.sub.5                                                                        n.sub.D.sup.29 1.5232                            16                                                                                     ##STR25##  COOC.sub.2 H.sub.5                                                                        m.p. 74.0                                        17     OCOCH.sub.2 Cl                                                                               "        n.sub.D.sup.30 1.5174                            18     OCOCH.sub.2 OCH.sub.3                                                                        "        n.sub.D.sup.30 1.5004                            19     OCOCH.sub.3 OC.sub.2 H.sub.5                                                                 "        n.sub.D.sup.29 1.4960                            20     OCOCH.sub.2 SCH.sub.3                                                                        "        n.sub.D.sup.30 1.5370                            21     OCOOCH.sub.3                                                                               COOCH.sub.3                                                                               m.p. 118.0                                       22       "         COOC.sub.2 H.sub.5                                                                        m.p. 87-88                                       23       "         COOC.sub.3 H.sub.7n                                                                       n.sub.D.sup.29 1.4950                            24       "         COOC.sub.3 H.sub.7i                                                                       n.sub.D.sup.26  1.4892                           25       "         COOC.sub.4 H.sub.9n                                                                       n.sub.D.sup.27.5 1.4963                          26       "         COOC.sub.4 H.sub.9i                                                                       n.sub.D.sup.27 1.4911                            27       "         COOCH.sub.2 CHCH.sub.2                                                                    n.sub.D.sup.21 1.5158                            28       "         COOC.sub.6 H.sub.13n                                                                      n.sub.D.sup.21 1.4750                            29     OCOOC.sub.2 H.sub.5                                                                        COOCH.sub.3                                                                               m.p. 53.2                                        30       "         COOC.sub.2 H.sub.5                                                                        m.p. 54.2                                        31       "         COOC.sub.3 H.sub.7n                                                                       n.sub.D.sup.28 1.4885                            32       "         COOC.sub.3 H.sub.7i                                                                       n.sub.D.sup.26 1.4820                            33       "         COOC.sub.4 H.sub.9n                                                                       n.sub.D.sup.28 1.4860                            34       "         COOC.sub.4 H.sub.9i                                                                       n.sub.D.sup.27 1.4752                            35       "         COOCH.sub.2 CHCH.sub.2                                                                    n.sub.D.sup.21 1.5052                            36     OCOOC.sub.3 H.sub.7n                                                                       COOCH.sub.3                                                                               n.sub.D.sup.27.5 1.4631                          37     OCOOC.sub.3 H.sub.7i                                                                         "        m.p. 81.8                                        38       "         COOC.sub.3 H.sub.7i                                                                       m.p. 59.8                                        39       "         COOC.sub.4 H.sub.9n                                                                       m.p. 69.6                                        40     OCOOC.sub.4 H.sub.9n                                                                       COOCH.sub.3                                                                               n.sub.D.sup.27.5 1.4853                          41       "         COOC.sub.3 H.sub.7i                                                                       m.p. 59.8                                        42                                                                                     ##STR26##  COOCH.sub.3                                                                               n.sub.D.sup.27.5 1.5558                          43       "         COOC.sub.3 H.sub.7i                                                                       n.sub.D.sup.28 1.5356                            44                                                                                     ##STR27##  COOCH.sub.3                                                                               m.p. 133-134                                     45     OCOSC.sub.2 H.sub.5                                                                        COOC.sub.2 H.sub.5                                                                        n.sub.D.sup.26.5 1.5370                          46     OCOSC.sub.3 H.sub.7i                                                                       COOCH.sub.3                                                                               m.p. 96-98                                       47       "         COOC.sub.2 H.sub.5                                                                        m.p. 47-49                                       48       "         COOC.sub.4 H.sub.9n                                                                       n.sub.D.sup.27 1.5160                            49     OCONHCH.sub.3                                                                              COOCH.sub.3                                                                               m.p. 172.4                                       50       "         COOC.sub.2 H.sub.5                                                                        m.p. 152-153                                     51       "         COOC.sub.3 H.sub.7n                                                                       m.p. 113.2                                       52       "         COOC.sub.3 H.sub.7i                                                                       m.p. 146.4                                       53       "         COOC.sub.4 H.sub.9n                                                                       m.p. 110.6                                       54       "         COOC.sub.4 H.sub.9i                                                                       m.p. 125-127                                     55        "        COOCH.sub.2 CHCH.sub.2                                                                    m.p. 120-123                                     56     OCONHC.sub.2 H.sub.5                                                                       COOCH.sub.3                                                                               m.p. 129-132                                     57       "         COOC.sub.2 H.sub.5                                                                        m.p. 115-116                                     58       "         COOC.sub.3 H.sub.7n                                                                       m.p. 100-102                                     59       "         COOC.sub.3 H.sub.7i                                                                       m.p. 100.7                                       60       "         COOC.sub.4 H.sub.9n                                                                       m.p. 108.7                                       61       "         COOC.sub.4 H.sub.9i                                                                       m.p. 124-125                                     62     OCONHC.sub.3 H.sub.7n                                                                      COOCH.sub.3                                                                               m.p. 152-154                                     63       "         COOC.sub.2 H.sub.5                                                                        m.p. 98.4                                        64       "         COOC.sub.3 H.sub.7n                                                                       m.p. 115-116                                     65       "         COOC.sub.3 H.sub.7i                                                                       m.p. 122.1                                       66       "         COOC.sub.4 H.sub.9n                                                                       m.p. 87.7                                        67       "         COOC.sub.4 H.sub.9i                                                                       m.p. 94-96                                       68     OCONHC.sub.3 H.sub.7i                                                                      COOCH.sub.3                                                                               m.p. 149-151                                     69       "         COOC.sub.2 H.sub.5                                                                        m.p. 125.9                                       70       "         COOC.sub.3 H.sub.7n                                                                       m.p. 112-114                                     71       "         COOC.sub.3 H.sub.7i                                                                       m.p. 134.6                                       72       "         COOC.sub.4 H.sub.9n                                                                       m.p. 127.5                                       73       "         COOC.sub.4 H.sub.9i                                                                       m.p. 127-129                                     74     OCONHC.sub.4 H.sub.9n                                                                      COOCH.sub.3                                                                               m.p. 133-137                                     75       "         COOC.sub.2 H.sub.5                                                                        m.p. 120-121                                     76       "         COOC.sub.3 H.sub.7n                                                                       m.p. 105-106                                     77       "         COOC.sub.3 H.sub.7i                                                                       m.p. 90.4                                        78       "         COOC.sub.4 H.sub.9n                                                                       m.p. 78.7                                        79       "         COOC.sub.4 H.sub.9i                                                                       m.p. 89-90                                       80     OCON(CH.sub.3).sub.2                                                                       COOC.sub.2 H.sub.5                                                                        m.p. 102.6                                       81       "         COOC.sub.3 H.sub.7n                                                                       n.sub.D.sup.26 1.5150                            82       "         COOC.sub.4 H.sub.9n                                                                       m.p. 67-69                                       83                                                                                     ##STR28##  COOCH.sub.3                                                                               m.p. 168-171                                     84       "         COOC.sub.2 H.sub.5                                                                        m.p. 169.9                                       85       "         COOC.sub.3 H.sub.7n                                                                       m.p. 163-164                                     86       "         COOC.sub.3 H.sub.7i                                                                       m.p. 149.8                                       87       "         COOC.sub.4 H.sub.9i                                                                       m.p. 166-167                                     88     OSO.sub.2 CH.sub.3                                                                         COOCH.sub.3                                                                               m.p. 131-132                                     89       "         COOC.sub.2 H.sub.5                                                                        n.sub.D.sup.28 1.5228                            90       "         COOC.sub.3 H.sub.7n                                                                       n.sub.D.sup.30 1.5132                            91       "         COOC.sub.3 H.sub.7i                                                                       n.sub.D.sup.27 1.510                             92       "         COOC.sub.4 H.sub.9n                                                                       n.sub.D.sup.28 1.5100                            93       "         COOC.sub.4 H.sub.9i                                                                       n.sub.D.sup.28 1.5083                            94     OSO.sub.2 C.sub.2 H.sub.5                                                                  COOC.sub.2 H.sub.5                                                                        n.sub.D.sup.30 1.5163                            95                                                                                     ##STR29##  COOCH.sub.3                                                                               m.p. 158-160                                     96       "         COOC.sub.2 H.sub.5                                                                        m.p. 125-127                                     97       "         COOC.sub.3 H.sub.7n                                                                       m.p. 83-86                                       98       "         COOC.sub.3 H.sub.7i                                                                       m.p. 116-117                                     99       "         COOC.sub.4 H.sub.9n                                                                       n.sub.D.sup.28 1.5435                            100      "         COOC.sub.4 H.sub.9i                                                                       n.sub.D.sup.26 1.5467                            101      "         COOCH.sub.2CH CH.sub.2                                                                    m.p. 65-66                                       102      "         COOCH.sub.2 CCH                                                                           n.sub.D.sup.21 1.5759                            103    OSO.sub.2 N(CH.sub.3).sub.2                                                                COOC.sub.3 H.sub.7n                                                                       n.sub.D.sup.30 1.4980                            104    OSO.sub.2 N(C.sub.2 H.sub.5).sub.2                                                         COOC.sub.2 H.sub.5                                                                        n.sub.D.sup.30 1.5080                            105                                                                                    ##STR30##    "        m.p. 96.2                                        106      "         COOC.sub.3 H.sub.7n                                                                       n.sub.D.sup.29 1.5600                            107      "         COOC.sub.4 H.sub.9i                                                                       n.sub.D.sup.28 1.5500                            108    OP(S)(OC.sub.2 H.sub.5).sub.2                                                              COOC.sub.2 H.sub.5                                                                        m.p. 105.6                                       109    OP(S)(OCH.sub.3).sub.2                                                                     COOCH.sub.3                                                                               m.p. 89.9                                        110    OCON(CH.sub.3).sub.2                                                                       COOC.sub.4 H.sub.9i                                                                       m.p. 94-95                                       111    OP(S)(OCH.sub.3).sub.2                                                                     COOC.sub.2 H.sub.5                                                                        m.p. 77.6                                        112      "         COOC.sub.3 H.sub.7n                                                                       m.p. 52.2                                        113    OCOCH.sub.2 Cl                                                                               "        n.sub.D.sup.22 1.5210                            114    OCOC.sub.2 H.sub.5                                                                           "        n.sub.D.sup.22 1.4980                            115    OCOCH.sub.2 OCH.sub.3                                                                         "       n.sub.D.sup.22 1.5017                            116    OCOCH.sub.2 SCH.sub.3                                                                        "        n.sub.D.sup.20 1.5389                            117    OCOC.sub.3 H.sub.7n                                                                          "        n.sub.D.sup.21 1.4912                            118    OCOCH.sub.2 OC.sub.2 H.sub.5                                                                 "        n.sub.D.sup.20 1.4972                            119    OCONHC.sub.2 H.sub.5                                                                       COOCH.sub.2 CHCH.sub.2                                                                    m.p. 113-114                                     120    OCONHC.sub.3 H.sub.7n                                                                        "        m.p. 103-104                                     121    OCOC.sub.3 H.sub.7n                                                                        COOC.sub.4 H.sub.9n                                                                       n.sub.D.sup.11 1.4887                            122    OCOC.sub.2 H.sub.5                                                                           "        n.sub.D.sup.11 1.4991                            123    OCOCH.sub.2 Cl                                                                               "        n.sub.D.sup.11 1.5168                            124    OCOCH.sub.2 OCH.sub.3                                                                        "        n.sub.D.sup.11 1.4992                            125    OCOCH.sub.2 OC.sub.2 H.sub.5                                                                 "        n.sub.D.sup.11 1.4921                            126    OCOCH.sub.2 SCH.sub.3                                                                        "        n.sub.D.sup.11 1.5340                            127    OCOC.sub.3 H.sub.7n                                                                        COOC.sub.2 H.sub.5                                                                        n.sub.D.sup.17 1.4974                            128    OCOCH.sub.2 Cl                                                                             COOCH.sub.2 CHCH.sub.2                                                                    n.sub.D.sup.19 1.5392                            129    OCOC.sub.2 H.sub.5                                                                           "        n.sub.D.sup.17 1.5160                            130    OCOC.sub.3 H.sub.7n                                                                          "        n.sub.D.sup.16 1.5073                            131    OCOCH.sub.2 OCH.sub.3                                                                        "        n.sub.D.sup.19 1.5231                            132    OCOCH.sub.2 OC.sub.2 H.sub.5                                                                 "        n.sub.D.sup.20 1.5080                            133    OCOCH.sub.2 SCH.sub.3                                                                        "        n.sub.D.sup.19 1.5542                            134    OCOCH.sub.2 OCH.sub.3                                                                      COOCH.sub.2 CCH                                                                           m.p. 86-87                                       135    OCOCH.sub.2 SCH.sub.3                                                                        "        m.p. 88-89                                       136    OCOCH.sub.2 OC.sub.2 H.sub.5                                                                 "        m.p. 71-72                                       137    OCOC.sub.2 H.sub.5                                                                         COOC.sub.3 H.sub.7i                                                                       m.p. 62.6                                        138    OCOC.sub.3 H.sub.7n                                                                          "        n.sub.D.sup.10.5 1.4858                          139    OCOCH.sub.2 OCH.sub.3                                                                        "        n.sub.D.sup.10 1.500                             140    OCOCH.sub.2 OC.sub.2 H.sub.5                                                                 "        n.sub.D.sup.10 1.4945                            141    OCOCH.sub.2 SCH.sub.3                                                                        "        n.sub.D.sup.10 1.5378                            142    OCOCH.sub.2 Cl                                                                               "        n.sub.D.sup.10 1.5177                            143    OCOCH.sub.2 OC.sub.2 H.sub.5                                                               COOCH.sub.3                                                                               m.p. 120.4                                       144    OCOCHCH.sub.2                                                                                "        n.sub.D.sup.22.5 1.5269                          145      "         COOC.sub.3 H.sub.7n                                                                       n.sub.D.sup.27 1.5165                            146    OCOCH.sub.2 Cl                                                                             COOCH.sub.3                                                                               m.p. 95.0                                        147    OCOCH.sub.2 OCH.sub.3                                                                        "        m.p. 99.6                                        148    OCOCHCH.sub.2                                                                                "        m.p. 83.0                                        149    OCOC.sub.2 H.sub.5                                                                           "        m.p. 64.5                                        150    OCOC.sub.4 H.sub.9t                                                                          "        m.p. 127.9                                       151    OCOC.sub.3 H.sub.7n                                                                          "        m.p. 45.1                                        152    OCOCHCHCH.sub.3                                                                              "        m.p. 131.6                                       153    OCOC.sub.3 H.sub.7i                                                                        COOCH.sub.3                                                                               m.p. 66.7                                        154    OCOCH.sub.3 COOCH.sub.2 CCH                                                                           m.p. 113.5                                       155    OCOCHCH.sub.2                                                                              COOCH.sub.2 CHCH.sub.2                                                                    n.sub.D.sup.23 1.5337                            156      "         COOCH.sub.2 CCH                                                                           m.p. 88.1                                        157    OCOC.sub.2 H.sub.5                                                                           "        m.p. 106.2                                       158    OCOCH.sub.2 SCH.sub.3                                                                      COOCH.sub.3                                                                               m.p. 79-80                                       __________________________________________________________________________

                  TABLE 1b                                                         ______________________________________                                          ##STR31##                                                                                                     Physicochemical                                                                data                                           Com-                            [m.p. (°C.) or                          pound                           refractive                                     No.   X             CH.sub.2 R  index n.sub.D ]                                ______________________________________                                         159   H             CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                         m.p. 79-80                                     160   COOCH.sub.3   "           n.sub.D.sup.19 1.5040                          161   CONHCH.sub.3  "           m.p. 87.5                                      162   COCH.sub.3    "           n.sub.D.sup.19 1.5021                          163   COCH.sub.2 Cl "           n.sub.D.sup.27 1.5123                          164   COCH.sub.2 OCH.sub.3                                                                         "           n.sub.D.sup.27 1.4902                          165   COCH.sub.2 SCH.sub.3                                                                         "           n.sub.D.sup.27 1.5288                          166   COC.sub.2 H.sub.5                                                                            "           n.sub.D.sup.27 1.4890                          167                                                                                   ##STR32##    "           n.sub.D.sup.27 1.4976                          168   H             CH.sub.2 CH.sub.2 OCH.sub.3                                                                m.p. 126.5                                     169   COCH.sub.3    "           m.p. 67.7                                      170   COCH.sub.2 OCH.sub.3                                                                         "           m.p. 81.2                                      171   COCH.sub.2 Cl "           m.p. 83.8                                      172   COCH.sub.2 SCH.sub.3                                                                         "           n.sub.D.sup.27 1.5060                          173                                                                                   ##STR33##    "           n.sub.D.sup.27 1.5190                          174   COCHCH.sub.2  "           n.sub.D.sup.27 1.5190                          175   COC.sub.2 H.sub.5                                                                            "           n.sub.D.sup.27 1.4897                          176   COOCH.sub.3   "           m.p. 92.1                                      177   H                                                                                             ##STR34##  m.p. 153-154                                   178   COCH.sub.3    "           m.p. 95.7                                      179   COOCH.sub.3   "           m.p. 103.4                                     180   COCH.sub.2 Cl "           m.p. 102.9                                     181                                                                                   ##STR35##    "                                                                                           ##STR36##                                     182                                                                                   ##STR37##    "           n.sub.D.sup.27 1.5366                          183   CONHC.sub.2 H.sub.5                                                                          "           m.p. 158-159                                   184                                                                                   ##STR38##    "           m.p. 145-148                                   185   CON(C.sub.2 H.sub.5).sub.2                                                                   "           n.sub.D.sup.27  1.5145                         186                                                                                   ##STR39##    CH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                         n.sub.D.sup.25 1.5781                          187                                                                                   ##STR40##    "           n.sub.D.sup.25 1.5088                          188                                                                                   ##STR41##    "           m.p. 80-81                                     189                                                                                   ##STR42##    "           n.sub.D.sup.31 1.5333                          190                                                                                   ##STR43##    "           n.sub.D.sup.30 1.4803                          191   COSC.sub.3 H.sub.7i                                                                          "           n.sub.D.sup.30 1.5126                          192                                                                                   ##STR44##    "           n.sub.D.sup.25 1.5399                          193                                                                                   ##STR45##    "           m.p. 67-68                                     194   SO.sub.2 CH.sub.3                                                                            "           n.sub.D.sup.21 1.5159                          195   SO.sub.2 N(CH.sub.3).sub.2                                                                   "           n.sub.D.sup.21 1.5012                          196                                                                                   ##STR46##    "           m.p. 129-130                                   197                                                                                   ##STR47##                                                                                    ##STR48##  n.sub.D.sup.24 1.5770                          198                                                                                   ##STR49##    "           n.sub.D.sup.24 1.5843                          199   SO.sub.2 C.sub.2 H.sub.5                                                                     "           n.sub.D.sup.24 1.5585                          200   SO.sub.2 N(CH.sub.3).sub.2                                                                   "           n.sub.D.sup.22 1.5664                          201                                                                                   ##STR50##    "           n.sub.D.sup.21 1.5954                          202   COSC.sub.4 H.sub.9n                                                                          "           n.sub.D.sup.24 1.5624                          203                                                                                   ##STR51##    "           n.sub.D.sup.24 1.5811                          204                                                                                   ##STR52##    "           n.sub.D.sup.20 1.5448                          ______________________________________                                    

                  TABLE 1c                                                         ______________________________________                                          ##STR53##                                                                                                     Physicochemical                                                                data                                                                           [m.p. (°C.) or                          Compound                        refractive                                     No.     X              R.sub.6  index n.sub.D ]                                ______________________________________                                         205     COCH.sub.3     CH.sub.3 m.p. 112-113                                   206     H              "        m.p. 250                                       207     CONHCH.sub.3   "        m.p. 159-160                                   208     CONHC.sub.2 H.sub.5                                                                           "        m.p. 118-121                                   209     CONHC.sub.4 H.sub.9n                                                                          "        m.p. 116-118                                   210     H              C.sub.2 H.sub.5                                                                         117-180 (dec.)                                 211     Na             "        m.p. >280                                      212     COCH.sub.3     "        m.p. 92-94                                     213     CONHCH.sub.3   "        144-146 (dec.)                                 214     CONHC.sub.2 H.sub.5                                                                           "        m.p. 92-94                                     215     CON(CH.sub.3).sub.2                                                                           "        n.sub.D.sup.27 1.5300                          216     COOC.sub.2 H.sub.5                                                                            "        m.p. 53-54                                     217     COOCH.sub.3    "        m.p. 70.4                                      218     CONHC.sub.3 H.sub.7n                                                                          "        m.p. 121-122                                   219     CONHC.sub.3 H.sub.7i                                                                          "        m.p. 137-140                                   220     CONHC.sub.4 H.sub.9n                                                                          "        m.p. 106-107                                   221                                                                                     ##STR54##     "        m.p. 131-133                                   222     COOCH.sub.3    CH.sub.3 m.p. 78.5                                      223     COOC.sub.2 H.sub.5                                                                            "        m.p. 64.2                                      224     COOC.sub.3 H.sub.7n                                                                           "        n.sub.D.sup.12.5 1.4981                        225     COC.sub.2 H.sub.5                                                                             C.sub.2 H.sub.5                                                                         n.sub.D.sup.10.5 1.5105                        226     COC.sub.3 H.sub.7n                                                                            "        n.sub.D.sup.10.5 1.5075                        227     COCH.sub.2 OCH.sub.3                                                                          "        n.sub.D.sup.10 1.5220                          228     COCH.sub.2 OC.sub.2 H.sub.5                                                                   "        n.sub.D.sup.10 1.5119                          229     COCH.sub.2 SCH.sub.3                                                                          "        m.p. 70.4                                      230     COCH.sub.2 Cl  "        n.sub.D.sup.21 1.5453                          231     COCH.sub.3     C.sub.3 H.sub.7n                                                                        m.p. 52.8                                      232     COOC.sub.2 H.sub.5                                                                            "        n.sub.D.sup.21.5 1.4990                        233     COOC.sub.3 H.sub.7n                                                                           "        n.sub.D.sup.21.5 1.4913                        234                                                                                     ##STR55##     C.sub.2 H.sub.5                                                                         n.sub.D.sup.25 1.5295                          235                                                                                     ##STR56##     "        m.p. 127-128                                   236                                                                                     ##STR57##     "        n.sub.D.sup.25 1.5060                          237                                                                                     ##STR58##     "        n.sub.D.sup.27 1.5458                          238                                                                                     ##STR59##     "        m.p. 98-101                                    239                                                                                     ##STR60##     "        n.sub.D.sup.27 1.5495                          240     COSC.sub.3 H.sub.7n                                                                           "        n.sub.D.sup.26 1.5386                          241     SO.sub.2 C.sub.2 H.sub.5                                                                      "        m.p. 102-103                                   242                                                                                     ##STR61##     "        m.p. 117-120                                   243     SO.sub.2 N(CH.sub.3).sub.2                                                                    "        m.p. 93-95                                     244                                                                                     ##STR62##     "        n.sub.D.sup.25 1.5630                          245                                                                                     ##STR63##     "        m.p. 81.4                                      ______________________________________                                    

                                      TABLE 1d                                     __________________________________________________________________________      ##STR64##                                                                       No.Compound                                                                          X                                                                                      ##STR65##                                                                                 Z      index n.sub.D ]refractive[m.p.                                                (°C.) ordataPhysicochemical            __________________________________________________________________________     246   H                                                                                        ##STR66##                                                                               COOCH.sub.3                                                                            m.p. 136-138                                  247   "        "         COOC.sub.2 H.sub.5                                                                     m.p. 147-148                                  248   "                                                                                        ##STR67##                                                                               "       m.p. 140-142                                  249   COCH.sub.3                                                                               ##STR68##                                                                               "       n.sub.D.sup.22 1.5710                         250   H        "         H       m.p. 152-154 (dec.)                           251   OCOCH.sub.3                                                                             "         "       n.sub.D.sup.23 1.5380                         252   "        "         COOC.sub.2 H.sub.5                                                                     n.sub.D.sup.21 1.5510                         253   OCOC.sub.2 H.sub.5                                                                      "         "       n.sub.D.sup.20 1.5195                         254   COCH.sub.2 OCH.sub.3                                                                    "         "       n.sub.D.sup.20 1.5392                         255   OCOC.sub.2 H.sub.5                                                                      "         H       n.sub.D.sup.18 1.5132                         256   COCH.sub.3                                                                              "         COOCH.sub.3                                                                            n.sub.D.sup.27 1.5595                         257   COC.sub.2 H.sub.5                                                                       "         "       n.sub.D.sup.27 1.5430                         258   OCOCH.sub.3                                                                             "         "       Rf(φH) 0.3                                259   OCOC.sub.2 H.sub.5                                                                      "         "       n.sub.D.sup.25 1.5483                         260   COC.sub.2 H.sub.5                                                                       "         COOC.sub.2 H.sub.5                                                                     n.sub.D.sup.26 1.5513                         261   SCOC.sub.3 H.sub.7n                                                                     "         "       n.sub.D.sup.28 1.5694                         262   COCH.sub.2 OC.sub.2 H.sub.5                                                             "         "       n.sub.D.sup.28 1.5328                         263   H        "         COOC.sub.3 H.sub.7i                                                                    m.p. 130-132                                  264   OCOCH.sub.3                                                                             "         "       Rf(φ) 0.37                                265   H        "         CO      m.p. 179-181                                  266   OCOC.sub.2 H.sub.5                                                                      "         "       n.sub.D.sup.26 1.5681                         267   COCH.sub.2 OCH.sub.3                                                                    "         COOCH.sub.3                                                                            n.sub.D.sup.26 1.5670                         268   COCHCHCH.sub.3                                                                          "         "       n.sub.D.sup.28 1.5930                         269                                                                                   ##STR69##                                                                              "         "       n.sub.D.sup.27 1.5608                         270   COCH.sub.2 SCH.sub.3                                                                    "         "       n.sub.D.sup.27 1.6020                         271   COCH.sub.2 OC.sub.2 H.sub.5                                                             "         "       n.sub.D.sup.27 1.5533                         272   COSC.sub.3 H.sub.7n                                                                     "         "       n.sub.D.sup.25 1.5772                         273                                                                                   ##STR70##                                                                              "         COOC.sub.2 H.sub.5                                                                     n.sub.D.sup.25 1.5645                         274   COCHCH.sub.2                                                                            "         "       n.sub.D.sup.25 1.5905                         275   COCH.sub.2 SCH.sub.3                                                                    "         "       n.sub.D.sup.27 1.5913                         276   COCH.sub.3                                                                              "         COOC.sub.3 H.sub.7i                                                                    n.sub.D.sup.26 1.5538                         277   COC.sub.2 H.sub.5                                                                       "                                                                                         ##STR71##                                                                             m.p. 179-180                                  278   OCOCH.sub.3                                                                             "         "       n.sub.D.sup.27 1.5762                         279   OCOC.sub.2 H.sub.5                                                                       ##STR72##                                                                               COOC.sub.2 H.sub.5                                                                     n.sub.D.sup.25 1.4991                         280   COCH.sub.2 OCH.sub.3                                                                    "         "       n.sub.D.sup.28 1.5508                         281   COCHCH.sub.2                                                                            "         "       n.sub.D.sup.26 1.5822                         282   OCOCH.sub.3                                                                             "         "       n.sub.D.sup.29 1.5578                         283   COCH.sub.3                                                                              "         "       n.sub.D.sup.29 1.5605                         284   H                                                                                        ##STR73##                                                                               "       m.p. 139-141                                  285   OCOC.sub.2 H.sub.5                                                                      "         "       n.sub.D.sup.26 1.5358                         286   OCOCH.sub.3                                                                             "         "       n.sub.D.sup.26 1.5470                         287   CON(CH.sub.3).sub.2                                                                     "         "       n.sub.D.sup.25 1.5382                         288   COCH.sub.3                                                                              "         "       m.p. 79-81                                    289   COCHCH.sub.2                                                                            "         "       n.sub.D.sup.26 1.5748                         290   SO.sub.2 CH.sub.3                                                                        ##STR74##                                                                               "       n.sub.D.sup.25 1.5439                         __________________________________________________________________________

                                      TABLE 1e                                     __________________________________________________________________________      ##STR75##                                                                                                  Physicochemical                                                                data                                                                           [m.p. (°C.) or                             Compound                     refractive                                        No.   X           R.sub.6    index n.sub.D ]                                   __________________________________________________________________________     291                                                                                   ##STR76##  C.sub.2 H.sub.5                                                                           m.p. 96.4                                         292                                                                                   ##STR77##  CH.sub.3   m.p. 161.2                                        293                                                                                   ##STR78##  "          m.p. 191.4                                        294                                                                                   ##STR79##  C.sub.2 H.sub.5                                                                           n.sub.D.sup.25.5 1.5150                           295   COCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                       "          n.sub.D.sup.25.5 1.4929                           296                                                                                   ##STR80##  "          m.p. 137.1                                        297                                                                                   ##STR81##  "          n.sub.D.sup.25.5 1.5221                           298                                                                                   ##STR82##  "          n.sub.D.sup.25.5 1.4916                           299                                                                                   ##STR83##  "          m.p. 132.8                                        300   COCH.sub.2 OCOCH.sub.3                                                                     "          n.sub.D.sup.25.5 1.5042                           301                                                                                   ##STR84##  C.sub.3 H.sub.7n                                                                          n.sub.D.sup.27 1.5050                             302                                                                                   ##STR85##  CH.sub.3   n.sub.D.sup.26 1.5204                             303                                                                                   ##STR86##  "          m.p. 91                                           304   COCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                       "          n.sub.D.sup.27 1.4970                             305                                                                                   ##STR87##  C.sub.2 H.sub.5                                                                           n.sub.D.sup.27 1.5270                             306   "           C.sub.3 H.sub.7n                                                                          n.sub.D.sup.27 1.5168                             307   COCH.sub.2 Br                                                                              C.sub.2 H.sub.5                                                                           n.sub.D.sup.27 1.5392                             308   "           C.sub.3 H.sub.7n                                                                          n.sub.D.sup.27 1.5333                             309                                                                                   ##STR88##  CH.sub.2CHCH.sub.2                                                                        n.sub.D.sup.27 1.5260                             310                                                                                   ##STR89##  "          n.sub.D.sup.27 1.5340                             311                                                                                   ##STR90##  C.sub.2 H.sub.5                                                                           n.sub.D.sup.28 1.4958                             312   COOCH.sub.2 CH.sub.2 Br                                                                    "          n.sub.D.sup.25 1.5252                             313   COOCH.sub.2 CH.sub.2 OCH.sub.3                                                             "          n.sub.D.sup.25 1.4949                             314   "           CH.sub.3   n.sub.D.sup.25 1.5006                             315                                                                                   ##STR91##  C.sub.2 H.sub.5                                                                           n.sub.D.sup.25 1.4909                             316   COOCH.sub.2 CHCH.sub.2                                                                     "          n.sub.D.sup.31 1.5031                             317   COOCH.sub.2 CCH                                                                            "          n.sub.D.sup.30 1.5058                             318                                                                                   ##STR92##  CH.sub.2 CHCH.sub.2                                                                       n.sub.D.sup.30 1.4990                             319   COOCH.sub.2 CH.sub.2 Cl                                                                    CH.sub.3   m.p. 94-100                                       320                                                                                   ##STR93##  "          m.p. 90                                           321                                                                                   ##STR94##  CH.sub.2 CCH                                                                              m.p. 133-134                                      322                                                                                   ##STR95##  "          n.sub.D.sup.30 1.5012                             323   COOCH.sub.2 CH.sub.2 F                                                                     CH.sub.3   m.p. 75-85                                        324                                                                                   ##STR96##  CH.sub.2 CHCH.sub.2                                                                       m.p. 124-125                                      325                                                                                   ##STR97##  CH.sub.2 CCH                                                                              m.p. 86-87                                        326   COCH.sub.2 OCH.sub.3                                                                       C.sub.5 H.sub.11n                                                                         n.sub.D.sup.28 1.4859                             327                                                                                   ##STR98##  C.sub.2 H.sub.5                                                                           m.p. 131.0                                        328                                                                                   ##STR99##  "          m.p. 106.0                                        329   COCH.sub.3  C.sub.5 H.sub.11n                                                                         n.sub.D.sup.26 1.4892                             330                                                                                   ##STR100## "          n.sub.D.sup.25 1.5277                             331                                                                                   ##STR101## "          n.sub.D.sup.28 1.5410                             332                                                                                   ##STR102## CH.sub.2 CCH                                                                              m.p. 176-177                                      333   COCH.sub.2 CH.sub.2 OC.sub.2 H.sub.5                                                       C.sub. 5 H.sub.11n                                                                        n.sub.D.sup.25 1.4885                             334   COCH.sub.2 SCH.sub.3                                                                       "          n.sub.D.sup.19 1.5377                             335   SO.sub.2 CH.sub.3                                                                          "          n.sub.D.sup.20 1.5072                             336   COCH.sub.2 OCOCH.sub.3                                                                     "          n.sub.D.sup.25 1.4822                             337                                                                                   ##STR103## "          n.sub.D.sup.23 1.5056                             338                                                                                   ##STR104## "          n.sub.D.sup.24 1.5160                             339   CON(CH.sub.3).sub.2                                                                        "          n.sub.D.sup.22 1.5082                             340                                                                                   ##STR105## "          n.sub.D.sup.22 1.5149                             341   COSC.sub.3 H.sub.7n                                                                        "          n.sub.D.sup.21 1.5179                             342   SO.sub.2 N(CH.sub.3).sub.2                                                                 "          n.sub.D.sup.20 1.5123                             343                                                                                   ##STR106## C.sub.6 H.sub.13n                                                                         n.sub.D.sup.29 1.4870                             __________________________________________________________________________

The compounds of the present invention can be formulated, when they are intended to be used as agricultural and horticultural fungicides, into any forms conventionally adopted in the art for these purposes, for example, such compositions as dust, wettable powder, emulsion, granule, microgranule and the like. The carrier material, used for the uniform distribution of the present compounds in effective amounts, may be either a liquid or particulate solid material, and is not limited to specific materials. Suitably usable solid carrier materials include, for example, various kinds of kaolin, clay, diatomaceous earth, talc, silica and the like. Suitably usable liquid carrier materials may be those which are inert solvents for the present active ingredient compounds and those which are non-solvents therefor but capable of dispersing or dissolving said active ingredient compounds by the aid of appropriate adjuvants used in combination therewith. Such liquid carrier materials include, for example, benzene, xylene, toluene, kerosene, alcohols, ketones, dimethyl sulfoxide, dimethylformamide and the like. By using such liquid carriers in admixture with appropriate surface active agents and other formulation aids, for example, spreading agents, sticking agents and the like, the present active ingredient compounds can be formulated into, and used as, aqueous solution or emulsions.

Furthermore, the compounds of the present invention can be used in admixture with other fungicides, insecticides, herbicides, plant growth regulators, etc. for the purpose of lessening the labor and of ensuring the controlling effect of the present compounds.

When operating in accordance with the present invention, effective amounts of the compounds or compositions of this invention are applied to the plants in any convenient fashion. The application of liquid and particulate solid compositions to plants can be carried out by conventional methods, e.g., power dusters, boom and hand sprayers and spray dusters. The compositions can also be applied from airplanes as a dust or a spray because of their effectiveness at low dosages.

The application of an effective amount of the compounds or compositions of this invention to the plant is essential for the practice of the present invention. The exact amount of active ingredient to be employed may vary depending on several factors including the response desired as well as the plant species to be treated and stage of development thereof, and the amount of rainfall as well as the specific type of compound used. Generally, however, the active ingredients are applied in amounts of from about 100 grams to about 1,000 grams per hectare.

Some examples are given below to illustrate the use as agricultural and horticultural fungicides of the compounds of the present invention in compositions of varied types, but it should be construed that both the active ingredient compounds of the present invention and additives usable in such compositions are not limited to those exemplified in these examples.

EXAMPLE 24 (Dust)

A homogeneous mixture of 2 parts of compound No. 7 and 98 parts of clay is pulverized to obtain a dust preparation containing 2% of the active ingredient.

EXAMPLE 25 (Wettable Powder)

A homogeneous mixture of 30 parts of compound No. 11, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylenenonylphenyl ether and 62 parts of clay is pulverized to obtain a wettable powder having uniformly and finely dispersed therein all the constituents including 30% of the finely divided active ingredient. This wettable powder, when it is actually applied to plants, is diluted to 600 to 1000 times with water and then sprayed over the plants.

EXAMPLE 26 (Emulsion)

By mixing 30 parts of compound No. 12 with, and dissolving in, 55 parts of methyl ethyl ketone and 15 parts of polyoxyethylenenonylphenyl ether, an emulsion containing 30% of the active ingredient is obtained. The emulsion, when it is actually applied to plants, is diluted to 600 to 1000 time with water and then sprayed over the plants.

EXAMPLE 27 (Granule)

A mixture of 5 parts of compound No. 15, 1.5 parts of lauryl sulfate, 1.5 parts of calcium lignin sulfate, 25 parts of bentonite, 67 parts of acid clay and 15 parts of water is kneaded with a kneading machine, followed granulation. The granules thus obtained are then dried with a fluidized drier to obtain a granule preparation containing 5% of the active ingredient.

EXAMPLE 28 (Dust)

A homogeneous mixture of 2 parts of compound No. 162 and 98 parts of clay is uniformly pulverized to obtain a dust preparation containing 2% of the active ingredient.

EXAMPLE 29 (Wettable Powder)

A homogeneous mixture of 30 parts of compound No. 163, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylenenonylphenyl ether and 62 parts of clay is pulverized to obtain a wettable powder having uniformly and finely dispersed therein all the constituents including 30% of the active ingredient. The wettable powder thus obtained, when it is actually used, is diluted 600 to 1000 times with water and then sprayed over plants.

EXAMPLE 30 (Emulsion)

By mixing 30 parts of compound No. 165 with, and dissolved in, 55 parts of methyl ethyl ketone and 15 parts of polyoxyethylenenonylphenyl ether, an emulsion containing 30% of the active ingredient is obtained. The emulsion thus obtained, when it is actually applied to plants, is diluted to 600 to 1000 times with water and then sprayed over the plants.

EXAMPLE 31 (Granule)

A mixture of 5 parts of compound No. 173, 1.5 parts of lauryl sulfate, 1.5 parts of calcium lignin sulfonate, 25 parts of bentonite, 67 parts of acid clay and 15 parts of water is kneaded with a kneading machine, followed by granulation. The granules thus obtained are then dried with a fluidized drier to obtain a granule preparation containing 5% of the active ingredient.

EXAMPLE 32 (Dust)

A homogeneous mixture of 2 parts of compound No. 220 and 98 parts of clay is uniformly pulverized to obtain a dust preparation containing 2% of the active ingredient.

EXAMPLE 33 (Wettable Powder)

A homogeneous mixture of 30 parts of compound No. 223, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylenenonylphenyl ether and 62 parts of clay is uniformly poulverized to obtain a wettable powder having uniformly and finely dispersed therein all the constituents including 30% of the active ingredient. The thus obtained wettable powder, when it is actually applied to plants, is diluted to 600 to 1000 times with water and then sprayed over the plants.

EXAMPLE 34 (Emulsion)

By mixing 30 parts of compound No. 225 with, and dissolved in, 55 parts of methyl ethyl ketone and 15 parts of polyoxyethylenenonylphenyl ether, an emulsion containing 30% of the active ingredient is obtained. The emulsion thus obtained, when it is actually applied to plants, is diluted to 600 to 1000 times with water and then sprayed over the plants.

EXAMPLE 35 (Granule)

A mixture of 5 parts of compound No. 232, 1.5 parts of lauryl sulfate, 1.5 parts of calcium lignin sulfonate, 25 parts of bentonite, 67 parts of acid clay and 15 parts of water is kneaded with a kneading machine, followed by granulation. The granules thus obtained are dried with a fluidized drier to obtain a granule preparation containing 5% of the active ingredient.

EXAMPLE 36 (Dust)

A homogeneous mixture of 2 parts of compound No. 252 and 98 parts of clay is uniformly pulverized to obtain a dust preparation containing 2% of the active ingredient.

EXAMPLE 37 (Wettable Powder)

A homogeneous mixture of 30 parts of compound No. 253, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylenenonylphenyl ether and 62 parts of clay is uniformly pulverized to obtain a wettable powder having uniformly dispersed therein all the constituents including 30% of the finely divided active ingredient. The wettable powder thus obtained, when it is actually applied to plants, is diluted to 600 to 1000 times with water and then sprayed over the plants.

EXAMPLE 38 (Emulsion)

By mixing 30 parts of compound No. 256 with, and dissolving in, 55 parts of methyl ethyl ketone and 15 parts of polyoxyethylenenonylphenyl ether, an emulsion containing 30% of the active ingredient. The emulsion thus obtained, when it is actually applied to plants, is diluted to 600 to 1000 times with water and then sprayed over the plants.

EXAMPLE 39 (Granule)

A mixture of 5 parts of compound No. 258, 1.5 parts of lauryl sulfate, 1.5 parts of calcium lignin sulfonate, 25 parts of bentonite, 67 parts of acid clay and 15 parts of water is kneaded with a kneading machine, followed by granulation. The granules thus obtained are dried with a fluidized drier to obtain a granule preparation containing 5% of the active ingredient.

EXAMPLE 40 (Dust)

A homogeneous mixture of 2 parts of compound No. 297 and 98 parts of clay is uniformly pulverized to obtain a dust preparation containing 2% of the active ingredient.

Example 41 (Wettable Powder)

A homogeneous mixture of 30 parts of compound No. 301, 3 parts of calcium alkylbenzenesulfonate, 5 parts of polyoxyethylenenonylphenyl ether and 62 parts of clay is uniformly pulverized to obtain a wettable powder having uniformly and finely dispersed therein all the constituents including 30% of the active ingredient. The wettable powder thus obtained, when it is actually applied to plants, is diluted to 600 to 1000 times with water and then sprayed over the plants.

EXAMPLE 42 (Emulsion)

By mixing 30 parts of compound No. 302 with, and dissolving in, 55 parts of methyl ethyl ketone and 15 parts of polyoxyethylenenonylphenyl ether, an emulsion containing 30% of the active ingredient is obtained. The emulsion thus obtained, when it is actually applied to plants, is diluted to 600 to 1000 times with water and sprayed over the plants.

EXAMPLE 43 (Granule)

A mixture of 5 parts of compound No. 305, 1.5 parts of lauryl sulfate, 1.5 parts of calcium lignin sulfonate, 67 parts of acid clay, 25 parts of bentonit and 15 parts of water is kneaded with a kneading machine, followed by granulation. The granules thus obtained are dried with a fluidized drier to obtain a granule preparation containing 5% of the active ingredient.

Control effects on various plant diseases of the compounds of the present invention, when they are used as agricultural and horticultural fungicides, are illustrated below with reference to test examples.

TEST EXAMPLE 1 Test for Control Effect on Paddy Rice Blast

Over the 3rd-leaf stage seedlings of paddy rice (variety: Asahi) soil cultured in a biscuit pot of 9 cm in diameter in a greenhouse was sprayed a test liquid prepared by diluting a wettable powder prepared according to the general procedure of Example 25 to a predetermined concentration with water. One day after the spraying of the test liquid, the seedings were inoculated by atomizing technique with a spore suspension of rice blast fungus (Pyricularia oryzae). Upon completion of the inoculation, the seedlings were kept overnight under humidified circumstances (at 95-100% relative humidity and 24°-25° C.). Five (5) days after the inoculation, the number of lesions per leaf of the third stage leaves was investigated and the preventive value was calculated on the basis of the following equation. Furthermore, the phytotoxic activity against the rice plant of the test compound was investigated according to a fixed numerical scale, the injury ratings of which are defined as mentioned below. The results obtained are as shown in Table 2. ##EQU1##

    ______________________________________                                         Injury rating:                                                                 ______________________________________                                         5:              Very severe phototoxicity                                      4:              Severe phototoxicity                                           3:              Great phototoxicity                                            2:              Moderate phototoxicity                                         1:              Slight phototoxicity                                           0:              No phototoxicity                                               ______________________________________                                    

                  TABLE 2                                                          ______________________________________                                                 Concentration Control                                                  Compound                                                                               of spray liquid                                                                              value    Degree of                                       No.     (ppm)         (%)      phytotoxicity                                   ______________________________________                                         1       200           89       0                                               2       "             84       0                                               3       "             100      0                                               4       "             100      0                                               5       "             83       0                                               6       "             93       0                                               7       "             100      0                                               8       "             99       0                                               10      "             80       0                                               11      "             100      0                                               12      "             87       0                                               13      "             82       0                                               14      "             100      0                                               15      "             100      0                                               17      "             75       0                                               19      "             75       0                                               20      "             86       0                                               22      "             94       0                                               23      "             100      0                                               24      "             100      0                                               25      "             75       0                                               26      "             100      0                                               27      "             80       0                                               28      "             75       0                                               29      "             91       0                                               30      "             85       0                                               31      "             75       0                                               32      "             100      0                                               34      "             87       0                                               35      "             76       0                                               36      "             100      0                                               37      "             80       0                                               38      "             91       0                                               39      "             100      0                                               40      "             79       0                                               41      "             95       0                                               42      "             89       0                                               44      "             81       0                                               45      "             75       0                                               47      "             75       0                                               48      "             100      0                                               49      "             94       0                                               51      "             100      0                                               52      "             100      0                                               53      "             75       0                                               54      "             84       0                                               55      "             97       0                                               56      "             75       0                                               58      "             100      0                                               59      "             100      0                                               61      "             100      0                                               62      "             100      0                                               63      "             100      0                                               65      "             100      0                                               66      "             75       0                                               67      "             97       0                                               69      "             100      0                                               70      "             88       0                                               71      "             100      0                                               72      "             75       0                                               73      "             100      0                                               74      "             88       0                                               75      "             96       0                                               76      "             75       0                                               77      "             81       0                                               78      "             79       0                                               79      "             75       0                                               80      "             75       0                                               81      "             80       0                                               82      "             77       0                                               83      "             75       0                                               84      "             75       0                                               86      "             87       0                                               87      "             95       0                                               88      "             85       0                                               89      "             75       0                                               90      "             83       0                                               91      "             99       0                                               92      "             98       0                                               93      "             100      0                                               94      "             75       0                                               96      "             86       0                                               98      "             95       0                                               99      "             75       0                                               100     "             83       0                                               103     "             82       0                                               104     "             75       0                                               105     "             75       0                                               107     "             93       0                                               108     "             75       0                                               109     "             82       0                                               110     "             75       0                                               111     "             75       0                                               112     "             85       0                                               113     "             96       0                                               114     "             100      0                                               115     "             100      0                                               116     "             100      0                                               117     "             100      0                                               118     "             100      0                                               119     "             93       0                                               120     "             100      0                                               121     "             75       0                                               122     "             94       0                                               123     "             100      0                                               124     "             100      0                                               125     "             100      0                                               127     "             100      0                                               128     "             100      0                                               129     "             100      0                                               130     "             90       0                                               131     "             100      0                                               132     "             100      0                                               133     "             93       0                                               134     "             86       0                                               135     "             78       0                                               136     "             75       0                                               137     "             100      0                                               138     "             75       0                                               139     "             100      0                                               140     "             100      0                                               141     "             81       0                                               142     "             100      0                                               143     "             100      0                                               144     "             100      0                                               145     "             100      0                                               146     "             100      0                                               147     "             100      0                                               148     "             100      0                                               149     "             100      0                                               151     "             100      0                                               152     "             99       0                                               153     "             100      0                                               155     "             100      0                                               156     "             100      0                                               157     "             100      0                                               158     "             100      0                                               159     "             71       0                                               160     "             82       0                                               162     "             83       0                                               164     "             97       0                                               166     "             77       0                                               167     "             93       0                                               168     "             87       0                                               169     "             78       0                                               170     "             87       0                                               171     "             98       0                                               172     "             100      0                                               173     "             100      0                                               174     "             84       0                                               175     "             80       0                                               176     "             100      0                                               177     "             83       0                                               178     "             75       0                                               179     "             75       0                                               180     "             100      0                                               181     "             100      0                                               182     "             90       0                                               183     "             95       0                                               184     "             100      0                                               185     "             100      0                                               186     "             100      0                                               187     "             95       0                                               188     "             90       0                                               189     "             100      0                                               190     "             90       0                                               191     "             99       0                                               192     "             100      0                                               193     "             100      0                                               194     "             99       0                                               195     "             100      0                                               196     "             100      0                                               197     "             100      0                                               198     "             100      0                                               199     "             100      0                                               200     "             100      0                                               201     "             100      0                                               202     "             95       0                                               203     "             100      0                                               204     "             100      0                                               216     "             75       0                                               217     "             81       0                                               218     "             84       0                                               219     "             82       0                                               220     "             100      0                                               221     "             88       0                                               222     "             100      0                                               223     "             100      0                                               224     "             100      0                                               225     "             100      0                                               226     "             75       0                                               229     "             75       0                                               232     "             100      0                                               233     "             100      0                                               234     "             100      0                                               235     "             100      0                                               236     "             96       0                                               237     "             100      0                                               238     "             95       0                                               239     "             100      0                                               240     "             89       0                                               241     "             100      0                                               242     "             100      0                                               243     "             90       0                                               244     "             100      0                                               245     "             75       0                                               246     "             100      0                                               247     "             90       0                                               248     "             80       0                                               249     "             97       0                                               250     "             80       0                                               251     "             80       0                                               252     "             100      0                                               253     "             100      0                                               254     "             100      0                                               255     "             100      0                                               256     "             100      0                                               257     "             100      0                                               258     "             85       0                                               259     "             100      0                                               260     "             100      0                                               262     "             100      0                                               263     "             100      0                                               264     "             100      0                                               265     "             100      0                                               267     "             100      0                                               268     "             80       0                                               269     "             100      0                                               270     "             100      0                                               273     "             100      0                                               274     "             100      0                                               275     "             100      0                                               276     "             100      0                                               277     "             100      0                                               278     "             100      0                                               279     "             100      0                                               280     "             100      0                                               281     "             100      0                                               282     "             100      0                                               283     "             100      0                                               284     "             100      0                                               285     "             100      0                                               288     "             100      0                                               289     "             100      0                                               290     "             100      0                                               291     "             75       0                                               292     "             75       0                                               293     "             75       0                                               294     "             99       0                                               295     "             75       0                                               296     "             75       0                                               297     "             100      0                                               298     "             100      0                                               299     "             75       0                                               300     "             92       0                                               301     "             92       0                                               302     "             100      0                                               303     "             100      0                                               304     "             100      0                                               305     "             79       0                                               306     "             75       0                                               307     "             83       0                                               308     "             75       0                                               309     "             100      0                                               310     "             90       0                                               311     "             100      0                                               312     "             95       0                                               313     "             98       0                                               314     "             100      0                                               315     "             95       0                                               316     "             100      0                                               317     "             95       0                                               318     "             92       0                                               319     "             100      0                                               320     "             100      0                                               321     "             100      0                                               322     "             92       0                                               323     "             100      0                                               324     "             90       0                                               325     "             91       0                                               326     "             100      0                                               327     "             100      0                                               328     "             88       0                                               329     "             97       0                                               330     "             100      0                                               331     "             90       0                                               332     "             93       0                                               333     "             100      0                                               334     "             94       0                                               335     "             100      0                                               336     "             91       0                                               337     "             100      0                                               338     "             100      0                                               339     "             100      0                                               340     "             91       0                                               341     "             100      0                                               342     "             99       0                                               343     "             100      0                                               Comparative                                                                            "             95       0                                               chemical                                                                       (EDDP)                                                                         Non-treated                                                                            --            0        --                                              ______________________________________                                          (Note)                                                                         ##STR107##                                                               

TEST EXAMPLE 2 Test for Control Effect on Paddy Rice Brown Spot

Over the 4th-true leaf stage seedlings of paddy rice (variety: Asahi) soil cultured in a porcelain pot of 9 cm in diameter in a greenhouse was sprayed a test liquid prepared by diluting the compound to a predetermined concentration with water. One day after completion of the spraying of the test liquid, the seedlings were inoculated with a spore suspension of rice brown spot fungus (Cochliobolus miyabeanus). Five (5) days after the inoculation, the number of lesions per leaf of the 4-stage true leaves was investigated and the preventive value was calculated on the basis of the following equation. Furthermore, the phytotoxic activity against the paddy rice plant of the test compound was investigated according to the same procedure as in Test Example 1. The results obtained are as shown in Table 3. ##EQU2##

                  TABLE 3                                                          ______________________________________                                                  Concentration Control                                                 Compound of spray liquid                                                                              value    Degree of                                      No.      (ppm)         (%)      phytotoxicity                                  ______________________________________                                         2        500           100      0                                              3        "             100      0                                              4        "             100      0                                              5        "             100      0                                              6        "             100      0                                              7        "             100      0                                              8        "             94       0                                              10       "             100      0                                              15       "             83       0                                              16       "             75       0                                              17       "             93       0                                              18       "             100      0                                              19       "             100      0                                              20       "             100      0                                              21       "             100      0                                              22       "             100      0                                              23       "             100      0                                              24       "             100      0                                              25       "             92       0                                              26       "             85       0                                              27       "             89       0                                              29       "             100      0                                              30       "             100      0                                              31       "             93       0                                              32       "             75       0                                              36       "             92       0                                              37       "             75       0                                              44       "             79       0                                              49       "             100      0                                              50       "             100      0                                              51       "             91       0                                              52       "             100      0                                              54       "             90       0                                              55       "             100      0                                              56       "             100      0                                              58       "             98       0                                              59       "             100      0                                              62       "             100      0                                              63       "             100      0                                              64       "             91       0                                              65       "             100      0                                              68       "             100      0                                              69       "             100      0                                              71       "             100      0                                              74       "             83       0                                              77       "             75       0                                              85       "             75       0                                              86       "             75       0                                              95       "             75       0                                              97       "             75       0                                              103      "             88       0                                              106      "             75       0                                              113      "             100      0                                              114      "             100      0                                              115      "             100      0                                              116      "             100      0                                              118      "             100      0                                              119      "             90       0                                              120      "             100      0                                              123      "             100      0                                              124      "             100      0                                              125      "             100      0                                              126      "             100      0                                              128      "             100      0                                              129      "             100      0                                              131      "             100      0                                              132      "             100      0                                              133      "             100      0                                              134      "             100      0                                              135      "             88       0                                              136      "             92       0                                              139      "             100      0                                              140      "             100      0                                              141      "             100      0                                              142      "             100      0                                              143      "             100      0                                              144      "             100      0                                              145      "             100      0                                              146      "             100      0                                              147      "             100      0                                              148      "             100      0                                              149      "             100      0                                              155      "             100      0                                              159      "             96       0                                              160      "             96       0                                              161      "             100      0                                              162      "             99       0                                              163      "             100      0                                              164      "             100      0                                              165      "             99       0                                              167      "             73       0                                              170      "             82       0                                              171      "             80       0                                              172      "             84       0                                              181      "             85       0                                              182      "             95       0                                              183      "             100      0                                              184      "             100      0                                              185      "             100      0                                              186      "             90       0                                              187      "             100      0                                              188      "             90       0                                              189      "             100      0                                              190      "             99       0                                              191      "             100      0                                              192      "             100      0                                              193      "             100      0                                              194      "             90       0                                              195      "             100      0                                              196      "             95       0                                              197      "             90       0                                              198      "             100      0                                              199      "             100      0                                              200      "             100      0                                              201      "             100      0                                              202      "             100      0                                              203      "             100      0                                              204      "             100      0                                              205      "             93       0                                              207      "             95       0                                              208      "             97       0                                              209      "             75       0                                              210      "             75       0                                              212      "             84       0                                              213      "             91       0                                              214      "             75       0                                              215      "             96       0                                              216      "             100      0                                              217      "             92       0                                              218      "             97       0                                              211      "             88       0                                              212      "             100      0                                              213      "             100      0                                              214      "             100      0                                              215      "             100      0                                              216      "             100      0                                              217      "             75       0                                              229      "             75       0                                              231      "             100      0                                              232      "             100      0                                              233      "             100      0                                              234      "             100      0                                              235      "             100      0                                              236      "             95       0                                              237      "             100      0                                              238      "             100      0                                              239      "             100      0                                              240      "             96       0                                              241      "             98       0                                              242      "             100      0                                              243      "             98       0                                              244      "             100      0                                              246      "             100      0                                              247      "             100      0                                              248      "             100      0                                              249      "             100      0                                              250      "             100      0                                              251      "             100      0                                              252      "             95       0                                              254      "             95       0                                              255      "             100      0                                              256      "             100      0                                              257      "             90       0                                              258      "             90       0                                              262      "             100      0                                              263      "             93       0                                              267      "             100      0                                              270      "             90       0                                              271      "             90       0                                              274      "             85       0                                              275      "             90       0                                              276      "             90       0                                              279      "             90       0                                              280      "             100      0                                              281      "             90       0                                              282      "             100      0                                              283      "             100      0                                              284      "             95       0                                              288      "             100      0                                              289      "             100      0                                              291      "             100      0                                              294      "             100      0                                              295      "             100      0                                              297      "             97       0                                              298      "             100      0                                              300      "             95       0                                              301      "             100      0                                              302      "             100      0                                              303      "             86       0                                              304      "             100      0                                              305      "             100      0                                              306      "             100      0                                              307      "             100      0                                              308      "             100      0                                              309      "             100      0                                              310      "             100      0                                              311      "             100      0                                              312      "             100      0                                              313      "             100      0                                              314      "             100      0                                              315      "             100      0                                              316      "             100      0                                              317      "             100      0                                              318      "             92       0                                              319      "             94       0                                              320      "             100      0                                              321      "             100      0                                              322      "             100      0                                              323      "             93       0                                              324      "             100      0                                              325      "             100      0                                              326      "             94       0                                              327      "             100      0                                              328      "             100      0                                              329      "             91       0                                              330      "             100      0                                              331      "             97       0                                              332      "             100      0                                              333      "             100      0                                              334      "             100      0                                              335      "             100      0                                              336      "             99       0                                              337      "             100      0                                              338      "             98       0                                              339      "             100      0                                              340      "             100      0                                              341      "             100      0                                              342      "             100      0                                              343      "             100      0                                              Comparative                                                                             "             90       0                                              chemical                                                                       (Triazine)                                                                     Non-treated                                                                             --            0        --                                             ______________________________________                                          (Note)                                                                         ##STR108##                                                               

TEST EXAMPLE 3 Test for Control Effect of Paddy Rice Sheath Blight

Over the 6th-leaf stage seedlings of paddy rice soil cultured in a porcelain pot of 9 cm in diameter was sprayed 40 ml per 3 pots of a test liquid of the compound having a predetermined concentration, and the seedlings thus treated were allowed to stand in a highly humidified glass chamber for weathering. One day after the spraying of the test liquid, inoculation conducted by patching each seedling at the second leaf sheath position with an agar disc obtained by perforating by means of a cork borer of 5 mm in diameter the edge of a colony of the pathogenic fungus (Pellicularia sasakii), which had previously been cultured (at 27° C. for 48 hours) on a potato sucrose agar medium, and the thus inoculated seedlings were kept in a moist chamber (at 95-100% relative humidity and 28° C.). Four days after the inoculation, outbreak of the disease was observed by investigating the lesion length per seedling and the preventive value (%) was obtained in comparison with the blank plot, according to the following equation. ##EQU3##

The test results obtained are as shown in Table 4.

                  TABLE 4                                                          ______________________________________                                                   Concentration                                                                               Control                                                 Compound  of spray liquid                                                                             value     Degree of                                     No.       (ppm)        (%)       phytotoxicity                                 ______________________________________                                         4         500          100       0                                             6         "            100       0                                             7         "            100       0                                             8         "            83        0                                             17        "            75        0                                             24        "            100       0                                             27        "            100       0                                             29        "            75        0                                             32        "            100       0                                             34        "            75        0                                             35        "            100       0                                             37        "            78        0                                             38        "            100       0                                             43        "            100       0                                             45        "            100       0                                             47        "            75        0                                             48        "            75        0                                             52        "            96        0                                             54        "            75        0                                             55        "            90        0                                             59        "            99        0                                             65        "            75        0                                             67        "            80        0                                             73        "            75        0                                             87        "            75        0                                             89        "            75        0                                             93        "            75        0                                             101       "            75        0                                             102       "            75        0                                             127       "            75        0                                             129       "            75        0                                             131       "            95        0                                             133       "            75        0                                             134       "            79        0                                             135       "            94        0                                             137       "            75        0                                             140       "            75        0                                             144       "            100       0                                             145       "            75        0                                             151       "            85        0                                             153       "            92        0                                             294       "            75        0                                             295       "            94        0                                             296       "            83        0                                             Comparative                                                                               65          90        0                                             chemical                                                                       (Neoasozine)                                                                   Non-treated                                                                              --           0         --                                            ______________________________________                                          (Note)                                                                         Neoasozine: Ammonium iron methanearsonate                                

TEST EXAMPLE 4 Test for Control Effect on Tomato Late Blight

Over the young seedlings of tomato (variety: Sekai-ichi, the second true leaf stage seedlings) soil cultured in a porcelain pot of 9 cm in diameter in a greenhouse was sprayed by means of a pressure sprayer a test liquid prepared by diluting to a predetermined concentration with water a wettable powder prepared according to the general procedure of Example 25. Three days after completion of the spraying of the test liquid, the leaves of treated seedlings were inoculated by dropping the zoosporangia suspension of pathogenic fungus (Phytophthora infestans) with a needle injector, said pathogenic fungus having previously been cultured on potato tubers at 20° C. for 3 days. After completion of the inoculation, the thus treated seedlings were kept in a humidified chamber (at 95-98% relative humidity), and three days thereafter, outbreak of the disease was observed and the control value (%) was calculated according to the following equation. Furthermore, the phytotoxicity against the tomato plant of the test compound was investigated according to the same procedure as in Test Example 1. ##EQU4##

The results obtained are as shown in Table 5.

                  TABLE 5                                                          ______________________________________                                                  Concentration Control                                                 Compound of spray liquid                                                                              value    Degree of                                      No.      (ppm)         (%)      phytotoxicity                                  ______________________________________                                         2        500           100      0                                              3        "             93       0                                              4        "             100      0                                              5        "             100      0                                              7        "             100      0                                              8        "             100      0                                              10       "             100      0                                              13       "             92       0                                              15       "             84       0                                              17       "             78       0                                              18       "             100      0                                              19       "             100      0                                              20       "             100      0                                              21       "             100      0                                              22       "             100      0                                              23       "             100      0                                              24       "             100      0                                              27       "             100      0                                              29       "             100      0                                              30       "             100      0                                              32       "             75       0                                              41       "             75       0                                              42       "             92       0                                              45       "             81       0                                              52       "             100      0                                              53       "             96       0                                              54       "             100      0                                              55       "             100      0                                              56       "             84       0                                              58       "             100      0                                              59       "             100      0                                              61       "             88       0                                              63       "             100      0                                              64       "             96       0                                              65       "             100      0                                              66       "             85       0                                              67       "             75       0                                              69       "             86       0                                              71       "             100      0                                              72       "             98       0                                              75       "             100      0                                              76       "             100      0                                              77       "             100      0                                              81       "             100      0                                              82       "             91       0                                              110      "             80       0                                              113      "             100      0                                              114      "             96       0                                              115      "             100      0                                              116      "             100      0                                              117      "             100      0                                              118      "             100      0                                              119      "             100      0                                              120      "             100      0                                              125      "             100      0                                              126      "             100      0                                              128      "             100      0                                              129      "             75       0                                              131      "             100      0                                              132      "             100      0                                              133      "             100      0                                              134      "             100      0                                              135      "             100      0                                              136      "             100      0                                              139      "             75       0                                              141      "             100      0                                              142      "             75       0                                              143      "             100      0                                              144      "             100      0                                              145      "             100      0                                              146      "             100      0                                              147      "             100      0                                              148      "             100      0                                              149      "             100      0                                              157      "             90       0                                              159      "             99       0                                              160      "             75       0                                              162      "             100      0                                              163      "             80       0                                              164      "             100      0                                              165      "             100      0                                              169      "             91       0                                              171      "             75       0                                              173      "             77       0                                              174      "             75       0                                              177      "             93       0                                              178      "             83       0                                              180      "             100      0                                              181      "             100      0                                              182      "             95       0                                              183      "             100      0                                              184      "             100      0                                              185      "             100      0                                              187      "             100      0                                              188      "             100      0                                              190      "             96       0                                              191      "             100      0                                              192      "             90       0                                              193      "             100      0                                              194      "             100      0                                              196      "             96       0                                              197      "             100      0                                              198      "             100      0                                              199      "             100      0                                              200      "             100      0                                              202      "             100      0                                              203      "             100      0                                              204      "             100      0                                              205      "             75       0                                              207      "             77       0                                              208      "             75       0                                              210      "             82       0                                              211      "             75       0                                              212      "             94       0                                              214      "             98       0                                              215      "             88       0                                              216      "             99       0                                              217      "             100      0                                              218      "             77       0                                              219      "             91       0                                              220      "             100      0                                              222      "             100      0                                              223      "             75       0                                              224      "             99       0                                              225      "             89       0                                              226      "             100      0                                              227      "             75       0                                              229      "             96       0                                              231      "             100      0                                              233      "             76       0                                              234      "             95       0                                              235      "             100      0                                              236      "             100      0                                              237      "             95       0                                              238      "             90       0                                              239      "             100      0                                              240      "             100      0                                              241      "             96       0                                              242      "             100      0                                              243      "             90       0                                              244      "             100      0                                              246      "             100      0                                              247      "             100      0                                              248      "             100      0                                              249      "             100      0                                              251      "             100      0                                              252      "             100      0                                              253      "             100      0                                              254      "             100      0                                              255      "             100      0                                              256      "             90       0                                              257      "             90       0                                              258      "             95       0                                              259      "             100      0                                              262      "             90       0                                              264      "             90       0                                              265      "             100      0                                              266      "             90       0                                              267      "             100      0                                              270      "             100      0                                              271      "             100      0                                              274      "             100      0                                              275      "             100      0                                              276      "             100      0                                              280      "             100      0                                              281      "             100      0                                              282      "             100      0                                              283      "             100      0                                              284      "             100      0                                              286      "             90       0                                              288      "             100      0                                              289      "             100      0                                              291      "             90       0                                              292      "             100      0                                              294      "             100      0                                              295      "             100      0                                              297      "             100      0                                              298      "             100      0                                              301      "             100      0                                              302      "             100      0                                              303      "             100      0                                              304      "             100      0                                              305      "             100      0                                              306      "             100      0                                              307      "             100      0                                              308      "             100      0                                              309      "             95       0                                              310      "             100      0                                              311      "             95       0                                              312      "             100      0                                              314      "             100      0                                              315      "             100      0                                              316      "             100      0                                              318      "             100      0                                              320      "             100      0                                              321      "             100      0                                              322      "             100      0                                              324      "             100      0                                              326      "             100      0                                              328      "             100      0                                              329      "             100      0                                              330      "             90       0                                              331      "             95       0                                              332      "             100      0                                              333      "             100      0                                              335      "             100      0                                              336      "             100      0                                              337      "             99       0                                              338      "             100      0                                              339      "             100      0                                              340      "             100      0                                              341      "             100      0                                              342      "             100      0                                              343      "             100      0                                              Comparative                                                                             "             95       0                                              chemical                                                                       (TPN)                                                                          Non-treated                                                                             --            0        --                                             ______________________________________                                          ##STR109##                                                               

TEST EXAMPLE 5 Test for Control Effect on Haricot Sclerotinia Rot

Over the seedlings of haricot (variety: Taisho Kintoki) soil cultured in a porcelain pot of 9 cm in diameter in a greenhouse was sprayed, when the first rue leaf completely developed, 15 ml each per pot of a test liquid of the compound diluted with water to a predetermined concentration. On the following day, the first trifoliate leaf was cut off and the each leaflet of trifoliate leaf were placed in a 15 cm petri dish kept under moist conditions by placeing a wet filter paper thereon and were inoculated on the center portion of each leaflet with a fungus-containing agar segment obtained by perforating by means of a cork borer of 8 mm in diameter an edge of a colony of a haricot sclerotinia rot (Sclerotinia sclerotiorum) cultured previously at 20° C. for 2 days in PSA medium. Three days after inoculation, the lesion diameter formed was measured by means of slide calipers and the control value (%) was obtained according to the following equation. Furthermore, the phytotoxicity against the haricot plant of the test compound was investigated according to the same procedure as in Test Example 1.

    Control value (%)=(1-B/A)×100

A=Lesion length in blank plot--diameter of inoculation source (8 mm)

B=Lesion length in treated plot--diameter of inoculation source (8 mm)

The results obtained are as shown in Table 6.

                  TABLE 6                                                          ______________________________________                                                  Concentration Control                                                 Compound of spray liquid                                                                              value    Degree of                                      No.      (ppm)         (%)      phytotoxicity                                  ______________________________________                                         1        200           81       0                                              3        "             100      0                                              4        "             75       0                                              5        "             100      0                                              6        "             94       0                                              7        "             100      0                                              17       "             72       0                                              19       "             90       0                                              20       "             75       0                                              22       "             95       0                                              23       "             81       0                                              25       "             95       0                                              27       "             100      0                                              29       "             75       0                                              30       "             78       0                                              33       "             75       0                                              45       "             75       0                                              51       "             75       0                                              52       "             79       0                                              65       "             75       0                                              67       "             75       0                                              89       "             75       0                                              96       "             100      0                                              103      "             79       0                                              113      "             100      0                                              114      "             93       0                                              115      "             100      0                                              116      "             100      0                                              118      "             100      0                                              119      "             75       0                                              120      "             75       0                                              123      "             100      0                                              124      "             100      0                                              125      "             100      0                                              127      "             75       0                                              128      "             100      0                                              131      "             100      0                                              132      "             100      0                                              134      "             100      0                                              135      "             100      0                                              136      "             100      0                                              139      "             100      0                                              140      "             100      0                                              142      "             100      0                                              146      "             82       0                                              205      "             75       0                                              206      "             75       0                                              216      "             75       0                                              217      "             100      0                                              218      "             84       0                                              219      "             75       0                                              220      "             100      0                                              221      "             100      0                                              223      "             86       0                                              224      "             100      0                                              225      "             75       0                                              226      "             75       0                                              234      "             80       0                                              235      "             75       0                                              241      "             75       0                                              243      "             80       0                                              244      "             80       0                                              246      "             100      0                                              247      "             100      0                                              248      "             100      0                                              249      "             100      0                                              252      "             90       0                                              254      "             90       0                                              280      "             90       0                                              287      "             90       0                                              304      "             98       0                                              Comparative                                                                             "             70       0                                              chemical                                                                       (Thiophanate-                                                                  methyl)                                                                        Non-treated                                                                             --            0        --                                             ______________________________________                                          (Note)-                                                                        ##STR110##                                                               

TEST EXAMPLE 6 Test for Control Effect on Cucumber Downy Mildew

The young seedlings of cucumber (variety: Sagami Hanjiro, the first true leaf stage seedlings) cultivated in a greenhouse were placed on a turn table, and thereover was sprayed by means of a spray gun a test liquid of a wettable powder prepared according to the general procedure of Example 25 and diluted with water to a predetermined concentration. On the following day, the seedlings were inoculated by atomizing technique with a suspension of spores of a cucumber downy mildew fungus (Pseudoperonospora cubensis) which had been sporulated on the affected leaves of cucumber were brushed away into deionized water containing 50 ppm of Tween 20 (polyoxyethylene sorbitan monolaurate), so that the spore concentration in the suspension became 20-30 spores per unit visible field under a microscope of 150 magnifications. After keeping in a fumidified chamber at 20° C. for 24 hours, the inoculated seedlings were placed in a greenhouse to accelerate infection. Five days after the inoculation, percent lesion area of each leaf was investigated and the control value (%) in a treated plot was calculated in comparison with a blank plot, according to the following equation. ##EQU5##

The results obtained are as shown in Table 7.

                  TABLE 7                                                          ______________________________________                                                   Concentration                                                                               Control                                                 Compound  of spray liquid                                                                             value     Degree of                                     No.       (ppm)        (%)       phytotoxicity                                 ______________________________________                                         1         500          100       0                                             2         "            100       0                                             5         "            100       0                                             6         "            100       0                                             10        "            100       0                                             18        "             78       0                                             19        "            100       0                                             20        "            100       0                                             21        "            100       0                                             22        "            100       0                                             23        "            100       0                                             24        "            100       0                                             25        "            100       0                                             26        "            100       0                                             29        "            100       0                                             30        "            100       0                                             31        "            100       0                                             32        "            100       0                                             49        "            100       0                                             50        "            100       0                                             51        "            100       0                                             52        "            100       0                                             53        "            100       0                                             54        "            100       0                                             56        "            100       0                                             57        "            100       0                                             58        "            100       0                                             59        "            100       0                                             60        "            100       0                                             61        "            100       0                                             62        "            100       0                                             63        "            100       0                                             64        "            100       0                                             65        "            100       0                                             66        "            100       0                                             67        "            100       0                                             68        "            100       0                                             69        "            100       0                                             70        "            100       0                                             71        "            100       0                                             72        "            100       0                                             73        "             94       0                                             74        "            100       0                                             75        "            100       0                                             76        "            100       0                                             77        "             90       0                                             78        "             97       0                                             114       "            100       0                                             122       "            100       0                                             129       "            100       0                                             137       "            100       0                                             143       "            100       0                                             144       "            100       0                                             145       "            100       0                                             146       "            100       0                                             147       "            100       0                                             148       "            100       0                                             149       "            100       0                                             160       "            100       0                                             163       "            100       0                                             178       "            100       0                                             179       "            100       0                                             166       "            100       0                                             169       "             85       0                                             170       "             93       0                                             174       "             87       0                                             175       "             80       0                                             205       "            100       0                                             207       "            100       0                                             208       "            100       0                                             209       "            100       0                                             211       "            100       0                                             213       "            100       0                                             214       "             90       0                                             215       "            100       0                                             217       "            100       0                                             219       "            100       0                                             221       "            100       0                                             222       "            100       0                                             223       "            100       0                                             225       "            100       0                                             227       "            100       0                                             228       "            100       0                                             229       "            100       0                                             230       "            100       0                                             231       "            100       0                                             232       "            100       0                                             233       "            100       0                                             234       "            100       0                                             236       "            100       0                                             238       "            100       0                                             240       "            100       0                                             242       "            100       0                                             244       "            100       0                                             245       "            100       0                                             252       "            100       0                                             253       "            100       0                                             254       "            100       0                                             255       "            100       0                                             256       "            100       0                                             257       "            100       0                                             258       "            100       0                                             259       "            100       0                                             260       "            100       0                                             262       "            100       0                                             263       "            100       0                                             264       "            100       0                                             265       "             90       0                                             267       "            100       0                                             268       "            100       0                                             269       "            100       0                                             270       "            100       0                                             271       "            100       0                                             272       "            100       0                                             273       "             95       0                                             274       "             90       0                                             275       "            100       0                                             276       "            100       0                                             278       "            100       0                                             279       "            100       0                                             280       "            100       0                                             281       "            100       0                                             283       "            100       0                                             284       "             90       0                                             285       "             95       0                                             286       "            100       0                                             287       "             90       0                                             288       "            100       0                                             289       "            100       0                                             290       "            100       0                                             291       "            100       0                                             292       "            100       0                                             293       "            100       0                                             294       "            100       0                                             295       "            100       0                                             296       "            100       0                                             297       "            100       0                                             298       "            100       0                                             299       "            100       0                                             300       "            100       0                                             301       "            100       0                                             302       "            100       0                                             303       "            100       0                                             304       "            100       0                                             305       "            100       0                                             306       "            100       0                                             307       "            100       0                                             308       "            100       0                                             309       "            100       0                                             310       "            100       0                                             311       "            100       0                                             312       "            100       0                                             313       "            100       0                                             314       "            100       0                                             315       "            100       0                                             316       "            100       0                                             317       "            100       0                                             318       "            100       0                                             319       "            100       0                                             320       "            100       0                                             321       "            100       0                                             322       "            100       0                                             323       "            100       0                                             324       "            100       0                                             325       "            100       0                                             326       "            100       0                                             327       "            100       0                                             328       "            100       0                                             329       "            100       0                                             330       "            100       0                                             331       "            100       0                                             332       "            100       0                                             333       "            100       0                                             334       "            100       0                                             335       "            100       0                                             336       "            100       0                                             337       "            100       0                                             338       "            100       0                                             339       "            100       0                                             340       "            100       0                                             341       "            100       0                                             342       "            100       0                                             343       "            100       0                                             Comparative                                                                              "            100       0                                             chemical                                                                       (TPN)                                                                          Non-treated                                                                              --           0         --                                            ______________________________________                                    

TEST EXAMPLE 7 Test for Control Effect on Cucumber Powdery Mildew

Over the first leaf stage seedlings of cucumber (variety: Sagami hanjiro) soil cultured in a porcelain pot of 9 cm in diameter in a greenhouse was sprayed 10 ml of a test solution of the compound diluted to a predetermined concentration. On the following day, the seedlings were inoculated by atomizing technique with a spore suspension of cucumber powdery mildew fungus (Erysiphe cicholrcearum). Ten days after the inoculation, percent lesion area (%) was investigated and the control value (%) was calculated according to the following equation. ##EQU6##

The results obtained are as shown in Table 8.

                  TABLE 8                                                          ______________________________________                                                  Concentration Control                                                 Compound of spray liquid                                                                              value    Degree of                                      No.      (ppm)         (%)      phytotoxicity                                  ______________________________________                                         165      200           100      0                                              172      "             100      0                                              224      "             100      0                                              226      "             93       0                                              232      "             80       0                                              233      "             92       0                                              234      "             100      0                                              235      "             96       0                                              236      "             90       0                                              237      "             100      0                                              238      "             100      0                                              239      "             88       0                                              240      "             92       0                                              241      "             100      0                                              242      "             100      0                                              243      "             88       0                                              244      "             93       0                                              296      "             100      0                                              297      "             100      0                                              298      "             100      0                                              Comparative                                                                             100           100      0                                              chemical                                                                       (Denmart)                                                                      Non-treated                                                                             --            0        --                                             ______________________________________                                          (Note)                                                                         ##STR111##                                                               

TEST EXAMPLE 8 Test for Control Effect on Pear Black Spot

The new shoots of pear (variety: Niju-seiki) was cut, leaving the developed leaves at the upper portion and then inserted into a 100 ml flask filled with 50 ml of water. Over the new shoots thus treated was sprayed 20 ml per two shoots a test liquid of the compound diluted to a predetermined concentration. On the following day, the shoots were inoculated by atomizing technique with a spore suspension of a pear alternaria leaf spot fungus (Alternaria kikuchiana), the spore concentration of which had been adjusted to become 50-60 spores per unit visible field under a microscope (Olympus) of 150 magnifications. After the inoculation, the shoots were kept in a humidified chamber at 25° C., and three days thereafter percent lesion area of each treated leaf was investigated and the control value (%) was calculated according to the following equation. Furthermore, the phytotoxicity against the pear tree of the test compound was investigated according to the same procedure as in Test Example 1. The results obtained are as shown in Table 9. ##EQU7##

                  TABLE 9                                                          ______________________________________                                                  Concentration Control                                                 Compound of spray liquid                                                                              value    Degree of                                      No.      (ppm)         (%)      phytotoxicity                                  ______________________________________                                         207      500           92       0                                              208      "             78       0                                              210      "             100      0                                              211      "             100      0                                              212      "             100      0                                              213      "             92       0                                              Comparative                                                                             "             90       0                                              chemical                                                                       (Captan)                                                                       Non-treated                                                                             --            0        --                                             ______________________________________                                          (Note)-                                                                        ##STR112##                                                               

TEST EXAMPLE 9 Test for Seed Treatment against "Bakanae" Disease of Rice

Artificially inoculated rice seeds were obtained by inoculating a concentrated spore suspension of Gibberella fujikuroi causing the "Bakanae" disease at the ear-sprouting stage of a rice plant, and the rice seeds thus obtained were subjected to seed selection with water and then air dried to prepare rice seeds to be used in the test. The test compounds used were prepared according to the general procedure of Example 25. The test rice seeds each weight 15 g, were put in a saran net bag. The seed disinfectation was conducted by immersing the unhulled rice-containing saran net bag at 15° C. for 24 hours in a test liquid, the proportion by volume of the test liquid and the infected rice seeds being 1:1. After completion of the disinfectation, the rice seeds were subjected to preimmersion at 15° C. for 4 days, followed by germination acceleration treatment at 30° C. for 24 hours. The rice seeds thus treated were densely seeded in granular cultivation soil according to a standard seedling box method and then placed in a room kept at 30° C. for 2 days, followed by cultivation in a plastic greenhouse, exercising necessary supervision. Thirty two (32) days after the seeding (the 5-leaf stage), the number of seedlings infected with rice "Bakanae" disease (elongated and dead seedlings) was visually investigated to obtain the infected seedling ratio, and the seed disinfection ratio was calculated according to the following equation. ##EQU8##

The results obtained are as shown in Table 10.

                  TABLE 10                                                         ______________________________________                                                               Seed                                                     Compound Concentration                                                                               disinfection                                                                             Degree of                                      No.      (ppm)        ratio (%) phytotoxicity                                  ______________________________________                                         1        1000         79        0                                              2        "            100       0                                              3        "            100       0                                              4        "            100       0                                              5        "            100       0                                              6        "            100       0                                              7        "            100       0                                              8        "            100       0                                              9        "            75        0                                              10       "            100       0                                              11       "            75        0                                              15       "            96        0                                              16       "            75        0                                              17       "            100       0                                              18       "            100       0                                              19       "            100       0                                              20       "            100       0                                              21       "            96        0                                              22       "            97        0                                              23       "            100       0                                              24       "            100       0                                              25       "            100       0                                              26       "            75        0                                              27       "            100       0                                              29       "            100       0                                              30       "            100       0                                              33       "            75        0                                              35       "            82        0                                              36       "            75        0                                              40       "            75        0                                              46       "            75        0                                              49       "            100       0                                              50       "            100       0                                              51       "            100       0                                              52       "            100       0                                              53       "            100       0                                              54       "            100       0                                              55       "            100       0                                              56       "            100       0                                              57       "            100       0                                              58       "            100       0                                              59       "            100       0                                              60       "            100       0                                              61       "            100       0                                              62       "            100       0                                              63       "            100       0                                              64       "            100       0                                              65       "            100       0                                              66       "            84        0                                              67       "            75        0                                              68       "            100       0                                              69       "            100       0                                              70       "            100       0                                              71       "            100       0                                              72       "            88        0                                              73       "            75        0                                              74       "            100       0                                              75       "            100       0                                              76       "            100       0                                              77       "            100       0                                              81       "            82        0                                              83       "            75        0                                              84       "            87        0                                              96       "            89        0                                              104      "            75        0                                              106      "            75        0                                              109      "            76        0                                              113      "            100       0                                              114      "            100       0                                              115      "            100       0                                              116      "            100       0                                              117      "            90        0                                              118      "            100       0                                              119      "            100       0                                              120      "            100       0                                              121      "            90        0                                              122      "            100       0                                              123      "            100       0                                              124      "            100       0                                              125      "            100       0                                              126      "            100       0                                              127      "            95        0                                              128      "            100       0                                              129      "            100       0                                              130      "            100       0                                              131      "            100       0                                              132      "            100       0                                              133      "            100       0                                              134      "            85        0                                              135      "            100       0                                              136      "            90        0                                              137      "            100       0                                              138      "            100       0                                              139      "            100       0                                              140      "            100       0                                              141      "            100       0                                              142      "            100       0                                              143      "            100       0                                              144      "            80        0                                              145      "            100       0                                              146      "            100       0                                              147      "            95        0                                              148      "            100       0                                              149      "            100       0                                              150      "            100       0                                              151      "            90        0                                              152      "            100       0                                              153      "            85        0                                              154      "            100       0                                              155      "            100       0                                              156      "            75        0                                              157      "            100       0                                              158      "            100       0                                              205      "            75        0                                              207      "            100       0                                              208      "            100       0                                              209      "            100       0                                              212      "            75        0                                              213      "            100       0                                              214      "            100       0                                              216      "            93        0                                              217      "            100       0                                              218      "            100       0                                              219      "            100       0                                              220      "            95        0                                              221      "            100       0                                              222      "            100       0                                              223      "            100       0                                              224      "            100       0                                              225      "            100       0                                              226      "            100       0                                              227      "            100       0                                              228      "            100       0                                              229      "            100       0                                              230      "            90        0                                              231      "            100       0                                              232      "            96        0                                              233      "            100       0                                              234      "            100       0                                              235      "            100       0                                              236      "            92        0                                              237      "            100       0                                              238      "            93        0                                              239      "            97        0                                              240      "            100       0                                              241      "            100       0                                              242      "            100       0                                              243      "            90        0                                              244      "            100       0                                              245      "            100       0                                              246      "            100       0                                              247      "            100       0                                              248      "            100       0                                              249      "            100       0                                              252      "            100       0                                              253      "            100       0                                              254      "            90        0                                              260      "            95        0                                              262      "            100       0                                              263      "            100       0                                              264      "            100       0                                              265      "            100       0                                              266      "            100       0                                              267      "            100       0                                              268      "            100       0                                              269      "            100       0                                              270      "            100       0                                              271      "            100       0                                              272      "            100       0                                              273      "            100       0                                              274      "            100       0                                              275      "            100       0                                              276      "            100       0                                              277      "            100       0                                              278      "            100       0                                              279      "            100       0                                              280      "            100       0                                              281      "            100       0                                              282      "            100       0                                              283      "            100       0                                              284      "            100       0                                              285      "            100       0                                              286      "            100       0                                              287      "            100       0                                              288      "            100       0                                              289      "            100       0                                              290      "            100       0                                              294      "            77        0                                              299      "            100       0                                              Comparative                                                                             "            95        0                                              chemical                                                                       (Benomyl)                                                                      Non-treated                                                                             --           0         --                                             ______________________________________                                          (Note)-                                                                        ##STR113##                                                               

TEST EXAMPLE 10 Test for Seed Treatment against Brown Spot of Rice

The test was conducted in the same manner as in Test Example 9 and using the test compounds prepared according to Example 6, except that rice seeds (variety: Asominori) naturally infected with a rice brown spot fungus were used as the test seed rice. Twenty five (25) days after the seeding (the 3rd-leaf stage), the number of infected seedlings was visually investigated to obtain the infected seedling ratio and thereby to calculate the seed disinfectation ratio (%) according to the following equation. ##EQU9##

The results obtained are as shown in Table 11.

                  TABLE 11                                                         ______________________________________                                                               Seed                                                     Compound Concentration                                                                               disinfection                                                                             Degree of                                      No.      (ppm)        ratio (%) phytotoxicity                                  ______________________________________                                         2        1000         100       0                                              3        "            100       0                                              4        "            100       0                                              5        "            100       0                                              7        "            100       0                                              10       "            100       0                                              18       "            100       0                                              20       "            100       0                                              22       "            100       0                                              23       "            100       0                                              24       "            100       0                                              30       "            100       0                                              50       "            100       0                                              51       "            100       0                                              52       "            100       0                                              57       "            100       0                                              58       "            100       0                                              59       "            100       0                                              63       "            100       0                                              64       "            100       0                                              65       "            100       0                                              69       "            100       0                                              143      "            100       0                                              146      "            100       0                                              147      "            100       0                                              148      "            100       0                                              149      "            100       0                                              205      "            96        0                                              207      "            96        0                                              208      "            97        0                                              213      "            94        0                                              215      "            100       0                                              216      "            100       0                                              217      "            99        0                                              218      "            98        0                                              221      "            92        0                                              222      "            100       0                                              223      "            100       0                                              224      "            100       0                                              225      "            100       0                                              226      "            100       0                                              231      "            100       0                                              232      "            100       0                                              233      "            95        0                                              234      "            100       0                                              235      "            100       0                                              236      "            95        0                                              237      "            100       0                                              238      "            100       0                                              239      "            100       0                                              240      "            96        0                                              241      "            97        0                                              242      "            100       0                                              243      "            100       0                                              244      "            100       0                                              Comparative                                                                             "            51        0                                              chemical                                                                       (TMTD)                                                                         Non-treated                                                                             --           0         --                                             ______________________________________                                          (Note)-                                                                        ##STR114##                                                               

TEST EXAMPLE 11 Test for Antifungal Activity against Various Pathogenic Fungi Causing Plant Diseases

The test compound is dissolved in acetone, and 1 ml of the solution and 20 ml of a medium (PSA medium pH 5.8) kept at about 60° C. are mixed together in a 9 cm diameter petri dish to prepare a compound-containing agar plate having a predetermined concentration. After evaporating the acetone while removing the upper cover of the Shale overnight, the compound-containing agar plate medium is inoculated by means of platinum loop with a spore suspension of the test fungus previously cultured in a slant medium. After culturing at 24° C. for 48 hours, the growth of the test fungus was investigated according to the following standard for determining the growth of fungus. The results obtained are as shown in Tables 12a and 12b.

Standard for determining the growth of fungus:

-: No growth of the fungus is recognized at all.

⊥: Formation of only few colonies is observed at the portion where the spore suspension has been applied to, while the growth of the fungus is markedly prohibited.

+: Formation of many colonies is observed at the portion where the spore suspension has been applied to, but the whole surface of the applied portion is not covered yet by colonies, and the growth of the fungus is markedly prohibited.

++: The growth of the fungus is observed practically all over the surface of the applied portion, but the degree of the growth of the fungus is moderately poor.

+++: The growth of the fungus is observed all over the surface of the applied portion, and the fungus normally grows.

                                      TABLE 12a                                    __________________________________________________________________________               Fusarium                                                             Compound                                                                             Conc.                                                                              oxysporum f.                                                                          Cladosporium                                                                          Glomerella                                                                           Alternaria                                                                           Pyricularia                                                                          Cochliobolus                                                                          Valsa                         No.   (ppm)                                                                              cucumerinum                                                                           fulvum cingulata                                                                            kikuchiana                                                                           oryzae                                                                               miyabeanus                                                                            mali                          __________________________________________________________________________      1    50  ⊥˜+                                                                        -      ⊥                                                                               -     -     -      -˜⊥                 2    "   -      -      -     -     -     -      -                              3    "   -      -      -     -     -     -      -                              4    "   -      -      -     -     -     -      -                              5    "   +      +      -     ⊥                                                                               -     -      +                              6    "   +      ++     ⊥                                                                               -     -     -      ++                             7    "   -      -      -     -     -     -      -                              8    "   -˜⊥                                                                        -      -     -     -     -      ⊥˜+                10    "   -      ⊥˜+                                                                        -     -     -     -      ±                          15    "   ±   ++     ⊥˜+                                                                       ⊥                                                                               -     -      ±                          17    "   -      ⊥˜-                                                                        -     -     -     -      -                             18    "   ±   +      -     -     -     -      ⊥˜+                19    "   -˜⊥                                                                        +      -     -     -     -      ⊥˜+                20    "   ⊥ +      -     -     -     -      ⊥˜+                21    "   +      ⊥˜+                                                                        -     -     -     -      ⊥˜+                22    "   -      -      -     -     -     -      -                             23    "   ⊥ -˜⊥                                                                        -     -     -     -      +                             24    "   -      -      -     -     -     -      -                             25    "   +       +˜++                                                                           +     +     -     ⊥ +                             26    "   +      ++     ±  ⊥˜+                                                                       -     -      +                             27    "   -      -      -     -     -     -      ±                          29    "   +      +      -     ⊥˜+                                                                       -     -      +                             30    "   +      +      -     -     -     -      +                             31    "   +      ++     ⊥                                                                               +     -     -      +                             32    "   +      ++     +     ⊥˜+                                   35    "   +      +      +     ⊥˜+     +                                                                 -     -      ++                            49    "   ⊥˜+                                                                        -      -     -˜⊥                                                                       -     -      ⊥                        50    "   -      -      -     -     -     -      ±                          51    "   -      -      -     -     -     -      -                             52    "   -      -      -     -     -     -      -                             53    "   ⊥ ⊥ -     -     -     -      ⊥˜+                54    "   ⊥ -      -     -     -     -      +                             55    "   -      -      -     -     -     -      -                             56    "   +      ⊥ -     ⊥                                                                               -     -       +˜++                   57    "   -      ⊥ -     -     -     -      -                             58    "   -      -      -     -     -     -      ⊥                        59    "   -      -      -     -     -     -      -                             60    "   -˜+                                                                             -˜+                                                                             -˜⊥                                                                       -˜⊥                                                                       -     -      -˜+                     61    "   ⊥˜+                                                                        -      -     -     -     -      +                             62    "   +      +      -     -˜⊥                                                                       -     -       +˜++                   63    "   -      ⊥ -     -     -     -      -                             64    "   -      -      -     -     -     -      ⊥˜+                65    "   -      -      -     -     -     -      -                             66    "    +˜++                                                                           ⊥˜+                                                                        -     -     -     -      +                             67    "   +      ±   -     -     -     -      +                             68    "   +      +      -     ⊥˜+                                                                       -     -       +˜++                   69    "   -      ⊥ -     -     -     -      -                             70    "   ⊥˜+                                                                        -˜+                                                                             -     -     -     -      ⊥˜+                71    "   -      -      -     -     -     -      -                             72    "   +      +      -˜⊥                                                                       -     -     -      +                             73    "   ⊥˜+                                                                        -      -     -     -     -      +                             74    "    +˜++                                                                           ⊥˜+                                                                        -     -     -     -       +˜++                   75    "    ⊥˜++                                                                      ⊥˜+                                                                        -˜⊥                                                                       -     -     -      ⊥˜+                76    "   -      -      -     -     -     -      ⊥˜+                77    "   -      -      -     -     -     -      -                             78    "    ⊥˜++                                                                      ⊥˜+                                                                        -˜⊥                                                                       -˜⊥                                                                       -     ⊥˜+                                                                         +˜++                   79    "   +      +      ⊥                                                                               -˜+                                                                            -     -      +                             84    "   ++     ++     +     +     -     -      +                             85    "   +      ++     -˜⊥                                                                        +˜++                                                                          -     -      ++                            86    "   +      ++     ⊥˜+                                                                       ⊥                                                                               -     -      +                             96    "   -      -      -     -     -     -      -                             __________________________________________________________________________

                                      TABLE 12b                                    __________________________________________________________________________     Compound                                                                             Conc.                                                                              Gibberella                                                                           Cladosporium                                                                          Glomerella                                                                           Alternaria                                                                           Pyricularia                                                                          Cochliobolus                                                                          Valsa                          No.   (ppm)                                                                              Fujikuroi                                                                            fulvum cingulata                                                                            kikuchiana                                                                           oryzae                                                                               miyabeanus                                                                            mali                           __________________________________________________________________________     113   20  -     ⊥ ⊥                                                                               -     -     -      +                              114   "   -     +      ⊥                                                                               -     -     -      ++                             115   "   -     -˜⊥                                                                        ⊥                                                                               -     -     -      ⊥                         116   "   -     ⊥ ⊥                                                                               -     -     -      +                              117   "   +     ++     ++    ++    -     +˜++                                                                            ++                             118   "   -     -      -     -     -     -      -˜+                      119   "   -     ⊥ ⊥                                                                               -     -     -      ⊥                         120   "   -     ⊥ ⊥                                                                               -     -     -      ⊥                         122   "   ⊥                                                                               ++     ⊥                                                                               ⊥                                                                               -     -      ++                             123   "   ⊥˜+                                                                       ++     ⊥                                                                               +     -     ⊥ +                              124   "   -     +      ⊥                                                                               -     -     -      +                              125   "   -     +      -     ⊥                                                                               -     -      +                              126   "   ⊥                                                                               +      ⊥                                                                               ⊥˜+                                                                       -     -      +                              127   "   +     ++     +     ++    -     -      +                              128   "   -     +      +     -     -     -      +                              129   "   -     +      ⊥˜+                                                                       -     -     -      +                              130   "   ++    ++     ++    ++    -     +      ++                             131   "   -     ⊥ ⊥                                                                               -     -     -      +                              132   "   -     +       ⊥˜++                                                                     -     -     -      +                              133   "   -     ++     ⊥                                                                               -     -     -      +                              134   "   +     +      +      +˜++                                                                          -     -      ++                             135   "   ++    +      +     ++    -     -      +                              136   "   ++    +      ++    ++    -     ⊥ ++                             137   "   -     +      ⊥                                                                               ⊥                                                                               -     -      +                              138   "   ++    ++     +     ++    +˜++                                                                           ++     ++                             139   "   -     ⊥ ⊥                                                                               -     -     -      ⊥                         140   "   -     ⊥ ⊥                                                                               -     -     -      ⊥                         141   "   -     ⊥ ⊥                                                                               -     -     -      +                              142   "   -     ⊥ ⊥                                                                               -     -     -      ⊥                         144   "   ⊥                                                                               ⊥˜+                                                                        ⊥                                                                               ⊥                                                                               -     -      ++                             145   "   -     -      -     -     -     -      ++                             146   "   ++    ⊥˜+                                                                        ⊥                                                                               ⊥˜+                                                                       -     -      ++                             147   "   ++    +      ⊥                                                                               ++    -     -      ++                             148   "   ++    +      -     ++    -     -      ++                             149   "   ++    ⊥˜+                                                                        -     ++    -     -      ++                             151   "   ++     +˜++                                                                           -     ++    -     -      ++                             155   "   ⊥                                                                               ⊥ ⊥                                                                               ⊥                                                                               -     -      ++                             156   "   ++    ++     ++    ++    -     -      ++                             157   "   ++    ++     ++    ++    -     -      ++                             158   "   +     ++     ⊥                                                                               ++    -     -      ++                             246   "   -     -      -     -     -     -      -                              247   "   -     ⊥ ⊥                                                                               -     -     -      -                              248   "   +     +      +     -     -     -      +                              249   "   -     +      ⊥                                                                               -     -     -      +                              252   "   -     ⊥ -     -     -     -      ⊥                         253   "   +     ++     +     +     -     -      ++                             256   "   ⊥                                                                               +      ⊥                                                                               -     -     -      +                              257   "   ⊥                                                                               +      +     ⊥                                                                               -     -      +                              258   "   ⊥                                                                               +      +     ⊥                                                                               -     -      +                              259   "   +     +      +     +     -     -      +                              260   "   -     +      -     -     -     -      +                              262   "   -     ⊥ ⊥                                                                               ⊥                                                                               -     ⊥ +                              263   "   -     ⊥ ⊥                                                                               ⊥                                                                               ⊥                                                                               ⊥ +                              264   "   -     -      ⊥                                                                               -     -     -      ⊥                         265   "   +     +      +     +     -     ⊥ +                              267   "   +     +      +     ⊥                                                                               -     -      +                              269   "   ++    +      +     +     -     -      +                              270   "   ⊥                                                                               ⊥ ⊥                                                                               ⊥                                                                               -     -      +                              271   "   +     +      +     +     -     -      +                              273   "   +     ++     +     +     -     -      +                              274   "   -     ⊥ ⊥                                                                               -     -     -      +                              275   "   ⊥                                                                               +      +     -     -     -      +                              276   "   -     +      +     +     -     -      +                              280   "   +     ⊥ +     ++    ⊥                                                                               +      +                              281   "   +     ⊥ -     +     -     -      ++                             282   "   ⊥                                                                               ⊥ ⊥                                                                               +     ⊥                                                                               ⊥ +                              283   "   -     -      ⊥                                                                               -     -     -      ⊥                         284   "   ⊥                                                                               ⊥ +     +     ⊥                                                                               -      +                              285   "   +     +      +     +     ⊥                                                                               -      +                              286   "   ⊥                                                                               ⊥ -     -     ⊥                                                                               ⊥ ⊥                         288   "   ⊥                                                                               ⊥ +     ⊥                                                                               -     -      +                              289   "   +     +      +     +     ⊥                                                                               -      +                              291   "   ⊥                                                                               +      ⊥                                                                               -     -     -      +                              294   "   -     +      -     -     -     -      +                              295   "   -     +      ⊥                                                                               -     -     -      +                              297   "   +     +      +     -     -     -      +                              298   "   -     ++     ⊥                                                                               -     -     -      +                              300   "   -     +      ⊥                                                                               -     -     -      +                              301   "   -     -      ⊥                                                                               -     -     -      ⊥                         303   "   +     +      +     ++    -     -      +                              304   "   +     ⊥ -     +     -     -      ⊥                         305   "   -     ⊥ -     -     -     -      ⊥                         306   "   -     -      -     -     -     -      +                              307   "   -     ⊥ -     -     -     -      +                              308   "   -     -      -     -     -     -      ⊥                         309   "   -     +      +     -     +     -      -                              310   "   -     +      +     ⊥                                                                               -     -      +                              311   "   +     +      ⊥                                                                               ⊥                                                                               -     ⊥ +                              312   "   -     ⊥ -     -     -     -      +                              313   "   ⊥                                                                               ⊥ ⊥                                                                               ⊥                                                                               -     -      +                              314   "   -     ⊥ -     -     -     -      +                              315   "   ⊥                                                                               +      ⊥                                                                               ⊥                                                                               -     -      +                              316   "   -     ⊥ -     -     -     -      +                              317   "   -     +      -     -     -     -      +                              318   "   ⊥                                                                               +      -     -     -     -      +                              319   "   -     ⊥ -     -     -     -      +                              320   "   -     ⊥ -     -     -     -      +                              322   "   +     +      ⊥                                                                               -     -     -      +                              323   "   -     ⊥ -     -     -     -      +                              324   "   ⊥                                                                               +      ⊥                                                                               -     -     -      +                              325   "   +     +      -     +     -     -      +                              326   "   ⊥                                                                               ⊥ ⊥                                                                               ⊥                                                                               -     -      +                              327   "   -     ⊥ -     -     -     -      +                              328   "   ⊥                                                                               ⊥ -     -     -     -      +                              329   "   +     +      ⊥                                                                               ⊥                                                                               -     -      +                              330   "   ⊥                                                                               +      -     -     ⊥                                                                               -      +                              332   "   ⊥                                                                               +      -     ⊥                                                                               -     -      +                              333   "   ⊥                                                                               +      -     -     -     -      ⊥                         334   "   +     +      ⊥                                                                               ⊥                                                                               -     -      +                              335   "   ⊥                                                                               +      -     +     -     -      +                              336   "   +     +      +     +     +     +      +                              339   "   ⊥                                                                               +      ⊥                                                                               -     -     -      +                              __________________________________________________________________________ 

What we claim is:
 1. A thiophene derivative of the general formula ##STR115## wherein X represents hydrogen atom, alkali metal, --NH₄, --COR₁ (in which R₁ represents phenyl, halophenyl, lower alkyl, lower alkenyl, lower alkoxy lower alkyl, lower alkylthio lower alkyl, lower haloalkyl, ##STR116## cycloalkyl, or lower alkylthio), --CO-lower alkyl-R₂ (in which R₂ represents lower alkylcarbonyloxy or lower alkoxycarbonyl), ##STR117## (in which n represents an integer of 4 to 6 inclusive), di-lower alkylcarbamoyl, mono-lower alkylcarbamoyl, cycloalkylcarbamoyl, --COOR₃ (in which R₃ represents lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower alkoxy lower alkyl, lower alkoxycarbonyl lower alkyl, phenyl, substituted phenyl or benzyl), --SO₂ R₄ (in which R₄ represents lower alkyl, lower alkyl-substituted phenyl or di-lower alkylamino) or ##STR118## (in which R₅ represents lower alkyl); Y represents COOR₆ (in which R₆ represents alkyl, lower alkenyl, lower alkynyl, lower alkoxy lower alkyl or benzyl), hydrogen atom or ##STR119## (in which p represents hydrogen atom, halogen atom or lower alkyl); and Z represents --COOR₆ (in which R₆ is as defined above), cyano or ##STR120## (in which p is as defined above), provided that both Y and Z are not --COOR₆ (in which R₆ represents alkyl, lower alkenyl or lower alkynyl) when X represents hydrogen atom, alkali metal or --NH₄.
 2. A thiophene derivative of the before-mentioned general formula according to claim 1, wherein X is taken as a group --COR₁ (in which R₁ is lower alkyl, lower alkoxy lower alkyl, or lower alkylthio lower alkyl), a group --COOR₃ (in which R₃ is lower alkyl) or mono-lower alkylcarbamoyl; Y is taken as a group --COOR₆ (in which R₆ is lower alkyl, lower alkenyl or lower alkynyl) or a group ##STR121## (in which p is hydrogen or halogen); and Z is taken as a group --COOR₆ as defined above.
 3. A thiophene derivative of the before-mentioned general formula according to claim 1, which is one member selected from: ##STR122##
 4. A compound according to claim 1, which is ##STR123##
 5. A fungicide for agricultural and horticultural purposes, characterized by containing as its active ingredient a thiophene derivative represented by the general formula ##STR124## wherein X represents hydrogen atom, alkalimetal, --NH₄, --COR₁ (in which R₁ represents phenyl, halophenyl, lower alkyl, lower alkenyl, lower alkoxy lower alkyl, lower alkylthio lower alkyl, lower haloalkyl, ##STR125## cycloalkyl or lower alkylthio), --CO-lower alkyl-R₂ (in which R₂ represents lower alkylcarbonyloxy or lower alkoxycarbonyl), ##STR126## (in which n represents an integer of 4 to 6 inclusive), di-lower alkylcarbamoyl, mono-lower alkylcarbamoyl, cycloalkylcarbamoyl, --COOR₃ (in which R₃ represents lower alkyl, lower alkenyl, lower alkynyl, lower haloalkyl, lower alkoxy lower alkyl, lower alkoxycarbonyl lower alkyl, phenyl, substituted phenyl or benzyl), --SO₂ R₄ (in which R₄ represents lower alkyl, lower alkyl-substituted phenyl or di-lower alkylamino) or ##STR127## (in which R₅ represents lower alkyl); Y represents --COOR₆ (in which R₆ represents alkyl, lower alkenyl, lower alkynyl, lower alkoxy lower alkyl, or benzyl), hydrogen atom or ##STR128## (in which p represents hydrogen atom, halogen atom or lower alkyl); and Z represents COOR₆ (in which R₆ is as defined above), cyano or ##STR129## (in which p is as defined above), provided that both Y and Z are not --COOR₆ (in which R₆ represents alkyl, lower alkyl or lower alkynyl) when X represents hydrogen atom, alkali metal or --NH₄.
 6. A fungicide according to claim 5, wherein the thiophene derivative is of the general formula defined before wherein X is taken as a group --COR₁ (in which R₁ is lower alkyl, lower alkoxy lower alkyl, or lower alkylthio lower alkyl), a group --COOR₃ (in which R₃ is lower alkyl) or mono-lower alkylcarbamoyl; Y is taken as a group --COOR₆ (in which R₆ is lower alkyl, lower alkenyl or lower alkynyl) or a group ##STR130## (in which p is hydrogen or halogen); and Z is taken as a group --COOR₆ as defined above.
 7. A fungicide according to claim 5, wherein said thiophene derivative is one member selected from: ##STR131##
 8. A fungicide as claimed in any one of claims 5 to 7, wherein said thiophene derivative is present in the amount of 0.1 to 80% by weight based on the total formulation.
 9. A fungicide as claimed in claim 8, wherein the form of the formulation is a dust and the content of the thiophene derivative is 0.1 to 5% by weight.
 10. A fungicide as claimed in claim 8, wherein the formulation is in the form of granules and the content of the thiophene derivative is 5 to 20% by weight.
 11. A fungicide as claimed in claim 8, wherein the formulation is in the form of wettable powder and the content of the thiophene derivative is 0.1 to 5% by weight.
 12. A fungicide as claimed in claim 8, wherein the formulation is in the form of emulsifiable concentrate and the content of the thiophene derivative is 10 to 40% by weight. 